WO2005093809A1 - Unit layer posttreating catalytic chemical vapor deposition apparatus and method of film formation therewith - Google Patents

Unit layer posttreating catalytic chemical vapor deposition apparatus and method of film formation therewith Download PDF

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Publication number
WO2005093809A1
WO2005093809A1 PCT/JP2005/005566 JP2005005566W WO2005093809A1 WO 2005093809 A1 WO2005093809 A1 WO 2005093809A1 JP 2005005566 W JP2005005566 W JP 2005005566W WO 2005093809 A1 WO2005093809 A1 WO 2005093809A1
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Prior art keywords
gas
unit layer
surface treatment
film
thin film
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PCT/JP2005/005566
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French (fr)
Japanese (ja)
Inventor
Makiko Kitazoe
Hiromi Itou
Shin Asari
Kazuya Saitou
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Ulvac, Inc.
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Publication date
Application filed by Ulvac, Inc. filed Critical Ulvac, Inc.
Priority to JP2006511534A priority Critical patent/JPWO2005093809A1/en
Priority to US10/593,444 priority patent/US20080050523A1/en
Publication of WO2005093809A1 publication Critical patent/WO2005093809A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/022—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being a laminate, i.e. composed of sublayers, e.g. stacks of alternating high-k metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/02277—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition the reactions being activated by other means than plasma or thermal, e.g. photo-CVD
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02337—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/318—Inorganic layers composed of nitrides
    • H01L21/3185—Inorganic layers composed of nitrides of siliconnitrides

Definitions

  • the present invention relates to a unit layer post-processing catalytic chemical vapor deposition apparatus using a catalytic chemical vapor deposition method in which a thin film is formed by performing a surface treatment after forming a film for each unit layer, and a film forming method thereof.
  • Various semiconductor devices, liquid crystal displays (LCDs), and the like are manufactured by forming a predetermined thin film on a substrate.
  • a CVD method such as a CVD method, a chemical vapor deposition method, or the like
  • the law is also used !!).
  • the catalytic CVD method can form a film at a lower temperature than the thermal CVD method, and has no problems such as damage to a substrate due to generation of plasma unlike the plasma CVD method. It is attracting attention as a film formation method for next generation semiconductor devices and display devices (such as LCDs).
  • a mixed gas containing silane gas (SiH) and ammonia gas (NH) is used as a source gas in a reaction vessel.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2002-367991
  • a silicon nitride film formed by a conventional catalytic CVD method as described in Patent Document 1 described above is used.
  • the oxide film has insufficient step coverage (step coverage) to improve the in-plane uniformity of the film thickness, and does not have good current-voltage (IV) withstand voltage characteristics, so there is room for improvement.
  • the present invention can improve the in-plane uniformity of a silicon nitride film or the like, improve the step coverage, and improve the film quality such as the IV withstand voltage characteristics, and can improve the film quality for each unit layer. It is an object of the present invention to provide a unit layer post-processing catalyst vapor deposition apparatus capable of forming a thin film by performing surface treatment after film formation, and a method of forming the same.
  • the invention according to claim 1 of the unit layer post-treatment catalytic chemical vapor deposition apparatus of the present invention is characterized in that a catalytic action of an exothermic catalyst body that is resistance-heated in a reaction vessel capable of evacuating.
  • the surface treatment may be a surface treatment with a thin-film component-containing gas other than silicon containing active species and a surface treatment with hydrogen gas containing active species. , Or both.
  • the invention according to claim 3 is characterized in that the exothermic catalyst is irradiated with hydrogen gas to regenerate the catalytic ability.
  • the invention according to claim 4 is characterized in that the surface treatment is a shift of or a combination of a pull-out process of an excessive thin film component and a direct addition process of the thin film component.
  • the invention according to claim 5 is characterized in that one of a nitrogen gas and a rare gas is used instead of the hydrogen gas.
  • the invention according to claim 6 is characterized in that the thin-film component-containing gas is any one of silicon hydride and silicon halide, and one or both of nitrogen and nitrogen hydride.
  • the invention according to claim 7 is characterized in that the gas containing the thin film component containing the active species in the surface treatment is nitrogen and / or hydride of nitrogen.
  • the invention according to claim 8 of the unit layer post-processing film forming method of the present invention forms a thin film on a substrate by utilizing the catalytic action of an exothermic catalyst that is resistance-heated in a vacuum-evacuable reaction vessel.
  • a catalytic chemical vapor deposition method wherein a flow rate of a thin film component-containing gas and a hydrogen gas is introduced in a pulsed manner and brought into contact with an exothermic catalyst to generate active species;
  • a process of performing a surface treatment irrespective of whether it is before or after another surface treatment process of performing a surface treatment. Is repeated to form a laminated thin film. To have.
  • the invention according to claim 9 is characterized in that, in addition to the above-described configuration, the process is repeated a plurality of times during one cycle to determine whether one of the surface treatment steps and the other surface treatment steps are! / ⁇ . It is a thing.
  • one or both of the one surface treatment step and the other surface treatment step and the film formation step of forming a thin film for each unit layer on the substrate are continuously processed. It is characterized by being performed.
  • An eleventh aspect of the present invention is characterized in that a residual gas is evacuated after a shift in a film forming process, one surface treatment process, and another surface treatment process.
  • the invention according to claim 12 is characterized in that one surface treatment step is a step of extracting excess thin film components and another surface treatment step is a step of adding thin film components. is there.
  • the invention described in claim 13 is characterized in that it is a step of performing a surface treatment with a thin-film component-containing gas other than silicon containing active species in the final process force of one cycle.
  • the invention according to claim 14 is characterized in that one of a nitrogen gas and a rare gas is used instead of the hydrogen gas.
  • the invention according to claim 15 is characterized in that the thin film component-containing gas is any one of silicon hydride and silicon halide, and one of or both nitrogen and nitrogen hydride. .
  • the invention according to claim 16 is characterized in that the thin film component-containing gas containing active species in the surface treatment is nitrogen gas and / or hydride of nitrogen.
  • the thin film component-containing gas is a monosilane gas and an ammonia gas, the film forming process forms a silicon nitride film for each unit layer on the substrate, and the other surface treatment process forms the active species. It is characterized in that the surface treatment of the silicon nitride film for each unit layer is carried out with ammonia gas containing.
  • the invention according to claim 18 is characterized in that the final step of one cycle is a step of performing a surface treatment with ammonia gas which is a thin-film component-containing gas containing active species.
  • the unit layer post-processing catalyst vapor deposition apparatus of the present invention can switch the gas introduction instantaneously, so that film formation can be performed for each unit layer, and surface treatment can be performed for each unit layer formed. It is possible to improve the uniformity of the in-plane film thickness, the step coverage, and the film quality.
  • the unit layer post-processing film forming method of the present invention since the surface treatment is performed after forming the film for each unit layer, a laminated thin film having improved in-plane uniformity of film thickness, improved step coverage, and improved film quality characteristics. Can be formed.
  • FIG. 1 is a schematic configuration diagram showing a unit layer post-processing catalytic chemical vapor deposition apparatus according to an embodiment of the present invention.
  • FIG. 2 is a diagram showing an example of a gas supply timing chart of the unit layer post-processing film forming method according to the present embodiment.
  • FIG. 3 is a view showing a gas supply timing chart.
  • FIG. 4 is a view showing a gas supply timing chart.
  • FIG. 5 is a view showing a gas supply timing chart.
  • FIG. 6 is a view showing a gas supply timing chart.
  • FIG. 7 is a view showing a gas supply timing chart.
  • FIG. 8 is a view showing a step coverage change when only NH supply is changed.
  • FIG. 10 is a graph showing pressure dependence of in-situ post treatment.
  • FIG. 11 is a view showing a hydrogen treatment effect at the time of composite post treatment.
  • FIG. 12 is a diagram showing gas atmosphere dependency during composite post processing.
  • FIG. 13 is a diagram showing the unit film thickness dependence of a stacked Cat-SiN film.
  • FIGS. 3A and 3B show a case in which a hydrogen gas surface treatment is prioritized, and FIG. 3B shows a case in which an ammonia gas surface treatment is prioritized.
  • FIG. 15 is a diagram showing the composition ratio of SiN formed on a 50A SiN film on a silicon substrate, where (a) shows a case where hydrogen gas surface treatment was performed first, and (b) shows an ammonia gas surface treatment. Indicates the case in which
  • FIG. 16 is a diagram showing gas introduction order dependence during post processing.
  • FIG. 17 is a diagram showing the hydrogen content of a single-layer film made of standard Cat-SiN, a laminated film formed by post-processing of a unit-formed Cat-SiN unit, and a single-layer film made of PECVD-SiN.
  • FIG. 18 is a diagram comparing the hydrogen content of each Cat-SiN film.
  • FIG. 19 is a view showing film forming conditions of a film forming method according to Example 1 and a conventional film forming method.
  • FIG. 20 is a view showing film forming conditions of a film forming method according to Example 2 and a conventional film forming method.
  • FIG. 21 is a view showing the results of measuring coverage and I-V electric breakdown voltage characteristics of each silicon nitride film formed by the film forming method according to Example 2 and the conventional film forming method.
  • FIG. 22 is a view showing film forming conditions of a film forming method according to Example 3 and a conventional film forming method.
  • FIG. 23 shows the measurement results of the in-plane uniformity of the film thickness and the corrosion resistance (etching rate) to an etching solution for each silicon nitride film formed by the film forming method according to Example 3 and the conventional film forming method.
  • FIG. 23 shows the measurement results of the in-plane uniformity of the film thickness and the corrosion resistance (etching rate) to an etching solution for each silicon nitride film formed by the film forming method according to Example 3 and the conventional film forming method.
  • the unit layer post-processing catalytic chemical vapor deposition apparatus of the present invention is used in a reaction vessel capable of evacuating.
  • a catalytic chemical vapor deposition system that forms a thin film on a substrate by utilizing the catalytic action of a resistively heated exothermic catalyst.
  • a gas supply that can introduce the thin film component-containing gas and hydrogen gas into the reaction vessel in a pulsed manner.
  • System and an exhaust system capable of vacuum evacuation and pressure control.
  • the thin film component-containing gas and hydrogen gas introduced in pulse form come into contact with the heat generating catalyst and decompose, forming a thin film for each unit layer on the substrate. Then, a thin film is formed by performing a surface treatment on the thin film for each unit layer.
  • FIG. 1 is a schematic configuration diagram showing a unit layer post-processing catalytic chemical vapor deposition apparatus according to an embodiment of the present invention.
  • the unit layer post-treatment catalyzing device 1 includes a reaction system 10, a gas supply system 11, and an exhaust system 13.
  • a gas introduction part 4 for introducing the raw material gas 3 into the reaction vessel 2 is provided.
  • a substrate holder 6 for mounting a substrate 5 is provided at a position facing the gas introduction part 4.
  • a heater 7 for heating the substrate 5 mounted on the substrate holder 6 to a predetermined temperature is provided.
  • the gas introduction section 4 between the gas introduction section 4 and the substrate holder 6 in the reaction vessel 2 has a catalytic action for heating and decomposing the source gas introduced from the gas introduction section 4.
  • a medium 8 is provided.
  • a gas outlet 15 is provided on the catalyst body 8 side of the gas introduction part 4 so that the ejected raw material gas 3 comes into contact with the catalyst body 8 immediately!
  • a high melting point metal wire such as a tungsten wire wound in a coil shape is used as the catalyst body 8.
  • the force is not limited to this.
  • iridium, rhenium, indium, molybdenum, tantalum, niobium, etc. can be used. And further, these alloys may be used.
  • the gas supply manifold 9 connected to the gas introduction unit 4 has a silane gas (Si H), ammonia gas (NH) and hydrogen gas (H), respectively.
  • SiH disilane
  • SiH trisilane
  • SiF silicon tetrafluoride
  • SiCl silicon tetrachloride
  • SiH C1 dichlorosilane
  • Nitrogen hydrides of compounds containing nitrogen such as H 2) can be used.
  • the thin-film component-containing gas contains steam.
  • a gas that is liquid at room temperature is a carrier gas used as a thin-film component-containing gas whose vapor pressure has been adjusted by publishing.
  • the mass flow rate of the source gas can be set and controlled instantaneously by the valve 34 and the second pneumatic operation valve 35 and supplied to the gas supply manifold 9.
  • the first pneumatic operation valve 34 and the second pneumatic operation valve 35 switch the rectangular pulse-shaped mass flow rate to the reaction vessel side while minimizing the fluctuation of the set flow rate.
  • the nitrogen gas introduction line 27 is connected to the purge of the reaction system 10 and the normal pressure after the film formation. Supply nitrogen gas used for recovery and the like.
  • the exhaust system 13 includes an auxiliary exhaust pump 41, a turbo molecular pump 43, a pressure control main knob 45, a sub-valve 47, and a vacuum gauge 49, and the reaction vessel 2 can be evacuated.
  • 51 indicates a relief valve
  • 53 indicates a manual valve
  • this line is a vent line at the time of normal pressure return.
  • the pressure control main valve 45 controls the degree of vacuum in the reaction vessel 2 by controlling the opening of the valve so as to reach a set pressure.
  • the reaction system 10, the gas supply system 11, and the exhaust system 13 are controlled by a computer, and the process sequence of opening / closing valves, setting the mass flow rate, supplying current to the catalyst, and the like in accordance with evacuation and gas introduction is not shown.
  • the user can set recipes such as operation panel power, process conditions and sequence processing.
  • 55 indicates a gate valve
  • 57 indicates a load lock chamber
  • the substrate 5 is carried into the reaction container 2 via the gate valve 55 and placed on the substrate holder 6.
  • the inside of the reaction vessel 2 is evacuated and purged with a hydrogen gas or a nitrogen gas, and then the pressure is controlled to a predetermined pressure with these purge gases.
  • the heater 7 is energized to perform resistance heating
  • the substrate 5 on the substrate holder 6 is heated to a predetermined temperature (for example, about 200 ° C. to 600 ° C.), and the catalyst body (such as a thin tungsten wire) 8 is energized.
  • the catalyst body 8 is heated to a predetermined temperature (for example, about 1600 ° C. to about 1800 ° C.).
  • the first pneumatic operation valve 34 is opened, and the second pneumatic operation valve 35 is closed to flow a predetermined set flow rate to the vent side to obtain a stable mass flow rate. Keep it. Then, the opening and closing of the first pneumatic operating valve 34 and the second pneumatic operating valve 35 are instantaneously switched, and the raw material gas (mixed gas of silane gas and ammonia gas, The gas (mass) is introduced in a rectangular pulse shape, and the raw material gas is ejected toward the catalyst 8 from a plurality of gas ejection ports 15 formed on the lower surface of the gas introduction unit 4.
  • the raw material gas is catalytically thermally decomposed by the heated catalyst 8, and a silicon nitride film is formed on the substrate 5, for example, with a monolayer as a unit layer (hereinafter, this film formation is performed). Process).
  • the film formation conditions at this time are as follows: a flow rate of silane gas (SiH 4) is 7 sccm, and an ammonia gas (NH 3)
  • the temperature of the catalyst body 8 is 1700 ° C., and in this embodiment, an ultra-thin silicon nitride film having a thickness of 1 nm is obtained in a single film-forming step of, for example, 10 seconds.
  • hydrogen gas is introduced into the gas introduction unit 4 through the gas supply manifold 9 for, for example, 15 seconds, and the hydrogen gas ejected from the gas ejection port 15 is heated.
  • the hydrogen gas ejected from the gas ejection port 15 is heated.
  • the surface of the silicon nitride film formed on the substrate 5 is exposed to the activated hydrogen gas, and the composition of the surface of the silicon nitride film is increased. Is improved (hereinafter, this step is referred to as one surface treatment step).
  • ammonia gas is introduced into the gas introduction unit 4 through the gas supply manifold 9 for, for example, 15 seconds, and the ammonia gas ejected from the gas ejection port 15 is heated. It is activated and supplied onto the substrate 5 via the catalyst 8.
  • instantaneous switching of gas introduction, pressure control, and high-speed vacuum evacuation can be performed, so that a thin-film component-containing gas and hydrogen gas can be introduced in a rectangular pulse shape. It can be decomposed by contact with the exothermic catalyst to form a thin film for each unit layer on the substrate, and the thin film for each unit layer can be surface-treated to form a laminated thin film.
  • This unit layer post-processing film formation method is a method in which resistive heating is performed in a reaction vessel that can be evacuated. This is a catalytic chemical vapor deposition method for forming a thin film on a substrate by utilizing the catalytic action of a thermal catalyst.
  • An active dangling process for generating a thin film for generating a thin film, a film forming process for forming a thin film for each unit layer on a substrate, a surface treatment process for performing a surface treatment of the thin film for each unit layer with hydrogen gas containing an active species, and an active species
  • the surface treatment of the thin film of each unit layer with the gas containing the thin film component containing is defined as one cycle, and a plurality of cycles are repeated to form a laminated thin film.
  • the process conditions are as follows: the temperature of the catalyst (Cat) wire, W (tungsten), is 1700 ° C, the substrate heater temperature is 100-300 ° C, and an 8-inch Si wafer is used as the substrate.
  • a silicon nitride film will be described as an example.
  • FIG. 2 is a diagram showing an example of a gas supply timing chart of the unit layer post-processing film forming method according to the present embodiment.
  • the unit layer post-processing film forming method according to the present embodiment is a SiH ZNH
  • the film forming process is continuously performed, and the post process and the film forming process are performed in one process.
  • Figures 3 to 7 show other examples of gas supply timing charts.
  • the common process conditions are as follows: the temperature of the heating catalyst is 1700 ° C and the pressure is lOPa.
  • Fig. 3 is a diagram showing film formation ⁇ hydrogen surface treatment ⁇ ammonia surface treatment ⁇ film formation ⁇ ' ⁇ ⁇
  • Fig. 4 shows film formation ⁇ ammonia surface treatment ⁇ hydrogen surface treatment ⁇ film formation ⁇ '
  • Figure 5 shows film formation ⁇ hydrogen surface treatment ⁇ ammonia surface treatment ⁇ hydrogen surface treatment ⁇ film formation ⁇ '
  • Fig. 6 shows film formation-> ammonia surface treatment-> hydrogen surface treatment-> ammonia surface treatment-> film formation-> Fig. 7 shows film formation-> vacuum evacuation-> hydrogen surface treatment-> ammonia surface treatment-> vacuum evacuation-> It is a figure which shows a film ⁇ ' ⁇ ⁇ ⁇ .
  • the introduction of hydrogen gas in the film formation process and the subsequent hydrogen surface treatment are performed continuously, and after the ammonia surface treatment, the introduction of ammonia gas in the film formation process is performed continuously.
  • the gas memory effect is extinguished by evacuating the atmosphere before and after the film forming process to remove the residual gas in the atmosphere.
  • the presence / absence of gas supply can be ensured.
  • film formation can be performed for each monolayer.
  • Figure 8 shows that the process conditions maintained the SiH / H supply constant ([7ZlO] sccm),
  • step coverage improvement is not gradual
  • the step coverage deteriorates again.
  • the step coverage improvement tends to disappear.
  • Figure 9 shows H and N as additive gases for improving step coverage under NH supply suppression.
  • the step coverage is much better when the added gas is hydrogen gas than nitrogen.
  • H is preferred as a type of additive gas for improving step coverage.
  • FIGS 8 and 9 show that the NH-derived Cat radical (Cat-NH) and the H-derived Cat radical
  • SiN film Cat One of the roles played by added H in the CVD system is Si-rich SiN
  • this is supposed to be nothing but the inhibition of the surface process of SiN during the deposition, and also contributes to the improvement of the step coverage through the shift of the system to the surface process rate-limiting side.
  • SiH C1 (dichlorosilane; DCS), Si CI (hexachlorodisilane; HCD), SiCl (four
  • saturated hydrogenated Si such as SiH and SiH is used as the Si source gas.
  • FIG. 10 shows the refractive index and unit layer of lOOnm-thick SiN in which about 100 lnm-thick SiN unit layers are stacked.
  • FIG. 6 is a graph showing the in-situ post-processing pressure dependence of a film forming rate per unit thickness and an 8-inch substrate in-plane film thickness distribution.
  • the refractive index, the film formation rate, and the in-plane film thickness uniformity hardly depend on the processing pressure, but the post-processing atmosphere (gas type), that is, the ammonia gas and hydrogen gas Differences have been shown to be affected.
  • the post-processing atmosphere is, for example, [A (20 seconds) ⁇ exhaust (5 seconds) ⁇ NH (10 seconds)]
  • the refractive index, the film formation rate per unit layer, and the film thickness distribution in the plane of the 8-inch substrate are significantly lower.
  • Figure 12 shows the gas atmosphere during "combined post-treatment" using both Cat-H irradiation and Cat-NH irradiation.
  • FIG. 13 shows the results of Cat-CVD by unit layer applying “composite post-processing” with optimized process conditions.
  • FIG. 9 is a diagram showing the dependence of the leakage current of a stacked SiN film on the unit layer thickness.
  • the leak current decreases as the unit layer thickness decreases! / Puru. Therefore, the smaller the deposited film thickness per cycle is, the more preferably the post-processing is performed for each unit layer in a unit of a monomolecular layer, the more the leak current is reduced and the electrical characteristics are improved.
  • FIG. 14 is a diagram showing the surface treatment depending on the gas type and the elemental profile in the thickness direction of the SiN film.
  • SiH and H are introduced at the same time 30 seconds after the introduction.
  • the film composition depends not only on the [Si substrate deposited film] interface but also on the type of gas introduced in advance. It is significantly different over the entire thickness direction.
  • Figures 15 (a) and (b) show the case where a Si substrate with a 5-nm-thick SiN film formed on the surface was used as the substrate, but it did not depend on the underlying SiN composition. The tendency is the same as in the case of direct film formation.
  • the properties of the entire deposited film are determined insensitively to the modification state and the material of the substrate surface.
  • the “surface” involved in the system is not only the substrate surface, which is the adsorbent for the generated radicals, but also the surface of the Cat wire, which is where radicals are produced. It has been suggested that the origin of this should be found in the process on the Cat line surface rather than the process on the substrate surface.
  • FIG. 16 is a diagram showing the dependence of the order of gas introduction during post processing.
  • the effect on the step coverage of the laminated SiN is that the step coverage changes completely depending on the order even if the refractive index is the same.To achieve a high step coverage, it is extremely effective to introduce ammonia as a post-process after forming a unit film. It is.
  • FIG. 17 shows a single-layer film made of standard Cat-SiN and a post-process of unit-layer Cat-SiN unit layer.
  • FIG. 4 is a diagram showing the hydrogen content of a laminated film and a single-layer film made of PECVD-SiN.
  • the film is formed by Cat-CVD, it will further decrease to about 2.2 x 10 21 cm- 3 .
  • FIG. 18 shows the effect of the addition of H, the suppression of NH supply, and the effect of the laminated film structure on the hydrogen content.
  • FIG. 1 A first figure.
  • the hydrogen content in the laminated SiN film with the Si-rich SiN film as the unit layer is determined by adding [H] and adding sufficient NH to the [SiH / NH] raw material.
  • VDSiN Rather less than in VDSiN, regardless of whether it is a laminated or single layer film.
  • the surface treatment process using hydrogen gas is a surplus Si bow I punching process and an addition process for supplementing the surface treatment power with ammonia gas.
  • the uniformity of the film thickness and the film quality can be improved by the process of compounding the above.
  • the final process of one cycle is treated with ammonia gas to make the step coverage much better.
  • the unit layer post-process film forming method according to the present embodiment can form a thin film having good in-plane film thickness uniformity, step coverage, and film quality.
  • Example 1 referring to FIG. 1, the heater 7 was energized and heated by resistance under a reduced pressure of lOPa to heat the substrate 5 on the substrate holder 6 to, for example, 200 ° C. (Electrical wire, etc.) 8 is heated by resistance, and the catalyst 8 is heated to 1700 ° C.
  • the film formation conditions are as follows: a flow rate of silane gas (SiH) is 7 sccm,
  • the flow rate of gas (NH 2) is 10 sccm
  • the flow rate of hydrogen gas (H 2) is 10 sccm
  • the force is 10 Pa
  • the temperature of the catalyst body 8 is 1700 ° C.
  • a thin film of silicon nitride having a thickness of lnm is obtained by one film forming process for 10 seconds.
  • the film forming step, one and other surface treatment steps are one cycle, and this one cycle of the film formation step, one and other surface treatment steps are continuously performed in this embodiment.
  • a silicon nitride film having a total thickness of 50 nm was finally formed.
  • the hydrogen concentration (hydrogen content) in the silicon nitride film measured by Fourier transform infrared spectrophotometer (FTIR) was 2 ⁇ 10 21 atomZcm 3 o
  • a silicon nitride film having a thickness of 50 nm formed in a single film forming step as in the conventional method was measured by a Fourier transform infrared spectrophotometer (FTIR).
  • FTIR Fourier transform infrared spectrophotometer
  • the hydrogen concentration in the silicon nitride film was 7 ⁇ 10 21 atomZcm 3 .
  • the conventional film forming conditions at this time are, as shown in FIG. 19, the flow rate of silane gas (SiH).
  • the pressure in the reaction vessel 2 is 10 Pa, and the temperature of the catalyst body 8 is 1700 ° C. (these conditions are the same as those of the film forming method in the embodiment of the present invention).
  • a silicon nitride film with a thickness of 50 nm is obtained in the film forming process.
  • the film forming step, one and other surface treatment steps of the present invention are defined as one cycle, and this one cycle of the film forming step, one and other surface treatment steps are continuously repeated a plurality of times. Therefore, according to the film forming method of the present invention for finally obtaining a silicon nitride film having a desired film thickness, the hydrogen concentration of the silicon nitride film obtained by the conventional film forming method is greatly reduced. Lower. Therefore, it is possible to provide a high-quality silicon nitride film having high reliability over a long period without increasing the leakage current when a high electric field is applied.
  • Example 1 a silicon nitride film having a thickness of lnm was formed in one film forming step, and this film forming step, one surface treatment step, and one cycle of another surface treatment step were continuously performed. A silicon nitride film having a thickness of 50 nm was finally formed by repeating 50 times.
  • a silicon nitride film having a thickness of 1 nm was formed in one cycle by the same deposition method as in the first embodiment. The film was formed, and this one cycle processing step was continuously repeated 100 times to finally form a silicon nitride film having a thickness of 10 Onm.
  • the flow rate of the silane gas (SiH 4) was 7 seconds.
  • ammonia gas (NH) flow rate is 10sccm
  • hydrogen gas (H) flow rate is 10sccm
  • the pressure in the reaction vessel 2 was 10 Pa, and the temperature of the catalyst body 8 was 1700 ° C (these conditions were the same as those in Example 1). Obtain a lnm silicon nitride film.
  • Example 2 As in Example 1, hydrogen gas was introduced in one surface treatment step, and ammonia gas was introduced in the other surface treatment steps.
  • the step coverage (%) and the current-voltage (IV) withstand voltage characteristics (MV / cm) of the silicon nitride film having a total film thickness of 100 nm obtained by the film forming method according to Example 2 were measured.
  • the side coverage of the silicon nitride film was 72%
  • the bottom force coverage was 90%
  • the withstand voltage of the IV electric characteristics was 4.8 MVZcm.
  • the coverage (%) and the current were compared for a 100 nm thick silicon nitride film formed in a single film forming process as in the conventional method.
  • the voltage (IV) withstand voltage (MV / cm) was measured, as shown in Fig. 21, the side coverage of the silicon nitride film was 72%, the bottom coverage was 90%, and the IV withstand voltage was 0.1mVZcm. It was obtained as follows.
  • the flow rate of the silane gas (SiH 4) was 7 sccm.
  • the flow rate of ammonia gas (NH) is 10 sccm
  • the flow rate of hydrogen gas (H) is 10 sccm
  • the pressure inside the reaction vessel 2 was 10 Pa and the temperature of the catalyst 8 was 1700 ° C (these conditions Under the same conditions as in the case of the film forming method in Example 2), a silicon nitride film having a thickness of ⁇ m is obtained in one film forming step.
  • the above-mentioned film forming step, one and other surface treatment steps are regarded as one cycle, and this one cycle of the film forming step, one surface treatment step and other surface treatment steps are continuously performed.
  • the film formation method according to the present invention in which a silicon nitride film having a desired film thickness is finally obtained by repeating a plurality of times, has improved step coverage over the silicon nitride film obtained by the conventional film formation method.
  • the IV withstand voltage characteristics have also been improved.
  • a silicon nitride film having a thickness of lnm is formed in one film forming step by the same film forming method as the second embodiment, and this film forming step, one surface treatment step, and other The surface treatment process was continuously repeated 100 times to finally form a silicon nitride film having a thickness of 100 nm.
  • the film formation conditions were such that the flow rate of silane gas (SiH) was 7 sccm,
  • the flow rate of ammonia gas (NH) is 10sccm
  • the flow rate of hydrogen gas (H) is 10sccm
  • Example 3 An extremely thin silicon nitride film having a thickness of 1 nm is obtained.
  • a silicon nitride film having a film thickness of 100 nm in a single film forming process as in the conventional method was compared with a silicon nitride film having a film thickness of 100 nm.
  • the measurement results shown in FIG. 6, that is, ⁇ 10% in-plane uniformity and an etching rate of 6 nm Zmin were obtained.
  • the film formation conditions were such that the flow rate of silane gas (SiH) was 7 sccc.
  • the flow rate of ammonia gas (NH) is 100 sccm
  • the flow rate of hydrogen gas (H) is Osccm
  • the pressure in the reaction vessel 2 is 10 Pa
  • the temperature of the catalyst body 8 is 1700 ° C.
  • a silicon nitride film having a thickness of 100 nm is obtained in one film forming step.
  • the film forming step, one surface treatment step, and another surface treatment step One cycle is performed, and the process of the one cycle is repeated a plurality of times continuously to finally obtain a silicon nitride film having a desired film thickness.
  • the in-plane uniformity of the film thickness of the silicon nitride film can be improved, and the corrosion resistance to the etchant can be improved.
  • the pressure in the reaction vessel 2 may be arbitrarily adjusted during the transition between the film forming step, one surface treatment step, and another surface treatment step in this one cycle.
  • one surface treatment step and another surface treatment step after the film formation step in this one cycle may be alternately repeated a plurality of times.
  • a stacked film can be formed in units of monomolecular layers, and the in-plane uniformity of the film thickness can be obtained. It is useful for forming a thin film with good step coverage and film quality.

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Abstract

A unit layer posttreating catalytic chemical vapor deposition apparatus that not only can enhance, with respect to silicon nitride films and the like, in-plane uniformity, step coverage and film quality but also for each unit layer, can perform surface treatment after film layer formation to thereby produce a thin film; and a method of unit layer posttreating film formation. There is provided a method for laminating of thin films posttreated for each unit layer, comprising repeating a cycle of steps consisting of the film formation step of introducing a mixed gas containing silane gas and ammonia gas as a raw gas in the form of rectangular pulse in reaction vessel (2) and performing catalytic pyrolysis of the raw gas by means of catalytic material (8) to thereby superimpose a silicon nitride film on substrate (5); the one surface treatment step of bringing ammonia gas into contact with the catalytic material (8) and realizing exposure of the surface of silicon nitride film on the substrate (5) to the ammonia gas; and the other surface treatment step of bringing hydrogen gas into contact with the catalytic material (8) and realizing exposure of the surface of silicon nitride film on the substrate (5) to the hydrogen gas.

Description

単位層ポスト処理触媒化学蒸着装置及びその成膜方法  Unit layer post-processing catalytic chemical vapor deposition apparatus and its film forming method
技術分野  Technical field
[0001] 本発明は、単位層ごとに成膜後、表面処理して薄膜を積層形成する触媒化学蒸着 法による単位層ポスト処理触媒化学蒸着装置及びその成膜方法に関する。  The present invention relates to a unit layer post-processing catalytic chemical vapor deposition apparatus using a catalytic chemical vapor deposition method in which a thin film is formed by performing a surface treatment after forming a film for each unit layer, and a film forming method thereof.
背景技術  Background art
[0002] 各種半導体デバイスや液晶ディスプレイ (LCD)等は、基板上に所定の薄膜を成膜 して製造されるが、その成膜方法として例えば CVD法 (ィ匕学気相成長法、化学蒸着 法とも!ヽぅ）が従来より用いられて!/ヽる。  [0002] Various semiconductor devices, liquid crystal displays (LCDs), and the like are manufactured by forming a predetermined thin film on a substrate. For example, a CVD method (such as a CVD method, a chemical vapor deposition method, or the like) is used. The law is also used !!).
[0003] CVD法としては、熱 CVD法、プラズマ CVD法などが従来より知られて!/、るが、近 年、加熱したタングステン等の素線 (以下、触媒体という）を触媒として利用し、反応 室内に供給される原料ガスを触媒体に接触させ分解することによって基板に堆積膜 を形成させる触媒 CVD法 (Cat— CVD法又はホットワイヤ CVD法とも呼ばれて ヽる） が実用化されている。  [0003] Thermal CVD, plasma CVD, and the like have been known as CVD methods in the past! / In recent years, recently, a heated element such as tungsten (hereinafter referred to as a catalyst) has been used as a catalyst. In addition, a catalytic CVD method (also called Cat-CVD method or hot-wire CVD method), which forms a deposited film on a substrate by bringing a raw material gas supplied into a reaction chamber into contact with a catalytic body and decomposing it, has been put into practical use. ing.
[0004] 触媒 CVD法は、熱 CVD法に比べて低温で成膜を行うことができ、また、プラズマ C VD法のようにプラズマの発生によって基板にダメージが生じる等の問題もないので、 次世代の半導体デバイスや表示デバイス (LCDなど)等の成膜方法として注目され ている。  [0004] The catalytic CVD method can form a film at a lower temperature than the thermal CVD method, and has no problems such as damage to a substrate due to generation of plasma unlike the plasma CVD method. It is attracting attention as a film formation method for next generation semiconductor devices and display devices (such as LCDs).
このような触媒 CVD法によりシリコン窒化膜を成膜する場合、従来ではシランガス ( SiH )およびアンモニアガス (NH )を含む混合ガスを原料ガスとして反応容器内に When a silicon nitride film is formed by such a catalytic CVD method, conventionally, a mixed gas containing silane gas (SiH) and ammonia gas (NH) is used as a source gas in a reaction vessel.
4 3 4 3
導入し、タングステンフィラメント等の触媒体を加熱して導入した原料ガスを接触させ 分解することによって、基板上に一度の成膜工程で必要膜厚のシリコン窒化膜を成 膜していた (例えば、特許文献 1参照)。  Then, by heating the catalyst body such as a tungsten filament and contacting the introduced source gas to decompose it, a silicon nitride film of the required thickness was formed on the substrate in a single film formation process (for example, Patent Document 1).
特許文献 1：特開 2002-367991号公報  Patent Document 1: Japanese Patent Application Laid-Open No. 2002-367991
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0005] しカゝしながら、上記特許文献 1のような従来の触媒 CVD法で成膜されるシリコン窒 化膜は、膜厚の面内均一性がよくなぐステップカバレッジ (段差被覆性)も不十分で あり、電流 電圧 (I V)耐圧特性もよいものが得られておらず、改善の余地がある。 そこで、本発明は、このような課題にかんがみ、シリコン窒化膜などの面内均一性の 向上、ステップカバレッジの向上及び I V耐圧特性などの膜質の向上を図ることがで きるとともに、単位層ごとに成膜後、表面処理して薄膜を積層形成することができる単 位層ポスト処理触媒蒸着装置及びその成膜方法を提供することを目的とする。 [0005] Meanwhile, a silicon nitride film formed by a conventional catalytic CVD method as described in Patent Document 1 described above is used. The oxide film has insufficient step coverage (step coverage) to improve the in-plane uniformity of the film thickness, and does not have good current-voltage (IV) withstand voltage characteristics, so there is room for improvement. In view of such problems, the present invention can improve the in-plane uniformity of a silicon nitride film or the like, improve the step coverage, and improve the film quality such as the IV withstand voltage characteristics, and can improve the film quality for each unit layer. It is an object of the present invention to provide a unit layer post-processing catalyst vapor deposition apparatus capable of forming a thin film by performing surface treatment after film formation, and a method of forming the same.
課題を解決するための手段  Means for solving the problem
[0006] 上記目的を達成するために本発明の単位層ポスト処理触媒化学蒸着装置のうち請 求項 1記載の発明は、真空排気可能な反応容器内で抵抗加熱した発熱触媒体の触 媒作用を利用して基板上に薄膜を形成する触媒化学蒸着装置であって、薄膜成分 含有ガス及び水素ガスの流量をパルス状に反応容器内に導入可能なガス供給系と 、真空排気かつ圧力制御可能な排気系とを備え、パルス状に導入された薄膜成分 含有ガス及び水素ガスが発熱触媒体に接触し分解し、基板上で単位層ごとの薄膜を 形成し、単位層ごとの薄膜に表面処理して積層薄膜を形成する構成を有して！/ヽる。  [0006] In order to achieve the above object, the invention according to claim 1 of the unit layer post-treatment catalytic chemical vapor deposition apparatus of the present invention is characterized in that a catalytic action of an exothermic catalyst body that is resistance-heated in a reaction vessel capable of evacuating. Is a catalytic chemical vapor deposition system that forms a thin film on a substrate by using a gas supply system that can introduce the flow rate of the gas containing thin film components and the flow rate of hydrogen gas into the reaction vessel in a pulsed manner, and enables vacuum evacuation and pressure control Gas and hydrogen gas, which are introduced in a pulsed manner, come into contact with the exothermic catalyst and decompose, forming a thin film for each unit layer on the substrate, and surface-treating the thin film for each unit layer To form a laminated thin film / Puru.
[0007] また請求項 2記載の発明は、上記構成に加え、表面処理が、活性種を含むシリコン を除く薄膜成分含有ガスによる表面処理及び活性種を含む水素ガスによる表面処理 の!、ずれか、或いは両方であることを特徴とするものである。  [0007] Further, in the invention according to claim 2, in addition to the above-mentioned configuration, the surface treatment may be a surface treatment with a thin-film component-containing gas other than silicon containing active species and a surface treatment with hydrogen gas containing active species. , Or both.
さらに請求項 3記載の発明は、発熱触媒体に水素ガスを照射して触媒能を再生さ せたことを特徴とするものである。  The invention according to claim 3 is characterized in that the exothermic catalyst is irradiated with hydrogen gas to regenerate the catalytic ability.
請求項 4記載の発明は、表面処理が、余剰薄膜成分の引き抜き処理及び薄膜成 分の直接的な添加処理の 、ずれか、或 、は両方であることを特徴とする。  The invention according to claim 4 is characterized in that the surface treatment is a shift of or a combination of a pull-out process of an excessive thin film component and a direct addition process of the thin film component.
請求項 5記載の発明は、水素ガスに代えて、窒素ガス及び希ガスのいずれかを用 いたことを特徴とする。  The invention according to claim 5 is characterized in that one of a nitrogen gas and a rare gas is used instead of the hydrogen gas.
請求項 6記載の発明は、薄膜成分含有ガスが、シリコンの水素化物及びシリコンの ハロゲン化物のいずれかと、窒素及び窒素の水素化物のいずれか、或いは両方とで あることを特徴とする。  The invention according to claim 6 is characterized in that the thin-film component-containing gas is any one of silicon hydride and silicon halide, and one or both of nitrogen and nitrogen hydride.
請求項 7記載の発明は、表面処理における活性種を含む薄膜成分含有ガスが窒 素及び窒素の水素化物の 、ずれか、或 、は両方であることを特徴とする。 [0008] 本発明の単位層ポスト処理成膜方法のうち請求項 8記載の発明は、真空排気可能 な反応容器内で抵抗加熱した発熱触媒体の触媒作用を利用して基板上に薄膜を形 成する触媒化学蒸着法であって、薄膜成分含有ガス及び水素ガスの流量をパルス 状に導入して発熱触媒体に接触させて活性種を発生させる活性ィ匕過程と、基板上で 単位層ごとの薄膜を形成する成膜過程と、活性種を含む水素ガスで単位層ごとの薄 膜の表面処理をする一の表面処理過程及び活性種を含む薄膜成分含有ガスで単 位層ごとの薄膜の表面処理をする他の表面処理過程の先後を問わず表面処理をす る過程とを備え、成膜後に表面処理をして単位層の薄膜を形成する一連の過程を一 サイクルとして、複数のサイクルを繰り返して積層された薄膜を形成する構成を有して いる。 The invention according to claim 7 is characterized in that the gas containing the thin film component containing the active species in the surface treatment is nitrogen and / or hydride of nitrogen. [0008] The invention according to claim 8 of the unit layer post-processing film forming method of the present invention forms a thin film on a substrate by utilizing the catalytic action of an exothermic catalyst that is resistance-heated in a vacuum-evacuable reaction vessel. A catalytic chemical vapor deposition method, wherein a flow rate of a thin film component-containing gas and a hydrogen gas is introduced in a pulsed manner and brought into contact with an exothermic catalyst to generate active species; A film forming process of forming a thin film of the same, a surface treatment process of performing a surface treatment of the thin film for each unit layer with hydrogen gas containing the active species, and a film forming process of the thin film for each unit layer with the gas containing the thin film component containing the active species. A process of performing a surface treatment irrespective of whether it is before or after another surface treatment process of performing a surface treatment. Is repeated to form a laminated thin film. To have.
[0009] また請求項 9記載の発明は、上記構成に加え、一の表面処理過程及び他の表面 処理過程の!/ヽずれかを一サイクル中に複数回の処理を繰り返すことを特徴とするも のである。  [0009] The invention according to claim 9 is characterized in that, in addition to the above-described configuration, the process is repeated a plurality of times during one cycle to determine whether one of the surface treatment steps and the other surface treatment steps are! / ヽ. It is a thing.
さらに請求項 10記載の発明は、一の表面処理過程及び他の表面処理過程のいず れか、或いは両方と、基板上で単位層ごとの薄膜を形成する成膜過程とが連続して 処理されることを特徴とするものである。  Further, in the invention according to claim 10, one or both of the one surface treatment step and the other surface treatment step and the film formation step of forming a thin film for each unit layer on the substrate are continuously processed. It is characterized by being performed.
請求項 11記載の発明は、成膜過程、一の表面処理過程及び他の表面処理過程 の 、ずれかの後に残留ガスを真空排気することを特徴とする。  An eleventh aspect of the present invention is characterized in that a residual gas is evacuated after a shift in a film forming process, one surface treatment process, and another surface treatment process.
請求項 12記載の発明は、一の表面処理過程が、余剰薄膜成分の引き抜き処理を する過程であり、他の表面処理過程が薄膜成分の添加処理をする過程であることを 特徴とするものである。  The invention according to claim 12 is characterized in that one surface treatment step is a step of extracting excess thin film components and another surface treatment step is a step of adding thin film components. is there.
[0010] 請求項 13記載の発明は、一サイクルの最終過程力 活性種を含むシリコンを除く 薄膜成分含有ガスで表面処理する過程であることを特徴とする。  [0010] The invention described in claim 13 is characterized in that it is a step of performing a surface treatment with a thin-film component-containing gas other than silicon containing active species in the final process force of one cycle.
請求項 14記載の発明は、水素ガスに代えて、窒素ガス及び希ガスのいずれかを用 いたことを特徴とする。  The invention according to claim 14 is characterized in that one of a nitrogen gas and a rare gas is used instead of the hydrogen gas.
請求項 15記載の発明は、薄膜成分含有ガスが、シリコンの水素化物及びシリコン のハロゲン化物のいずれかと、窒素及び窒素の水素化物のいずれか、或いは両方と であることを特徴とするものである。 請求項 16記載の発明は、表面処理における活性種を含む薄膜成分含有ガスが窒 素ガス及び窒素の水素化物の 、ずれか、或いは両方であることを特徴とする。 請求項 17記載の発明は、薄膜成分含有ガスがモノシランガス及びアンモニアガス であり、成膜過程がシリコン窒化膜を基板上で単位層ごとに形成するものであり、他 の表面処理過程が活性種を含むアンモニアガスで単位層ごとのシリコン窒化膜の表 面処理をするものであることを特徴とする。 The invention according to claim 15 is characterized in that the thin film component-containing gas is any one of silicon hydride and silicon halide, and one of or both nitrogen and nitrogen hydride. . The invention according to claim 16 is characterized in that the thin film component-containing gas containing active species in the surface treatment is nitrogen gas and / or hydride of nitrogen. In the invention according to claim 17, the thin film component-containing gas is a monosilane gas and an ammonia gas, the film forming process forms a silicon nitride film for each unit layer on the substrate, and the other surface treatment process forms the active species. It is characterized in that the surface treatment of the silicon nitride film for each unit layer is carried out with ammonia gas containing.
請求項 18記載の発明は、一サイクルの最終過程が、活性種を含む薄膜成分含有 ガスであるアンモニアガスで表面処理する過程であることを特徴とする。  The invention according to claim 18 is characterized in that the final step of one cycle is a step of performing a surface treatment with ammonia gas which is a thin-film component-containing gas containing active species.
発明の効果  The invention's effect
[0011] 本発明の単位層ポスト処理触媒蒸着装置は、瞬時のガス導入の切り換えが可能で あるので、単位層ごとの成膜を行うことができるとともに、成膜した単位層ごとに表面 処理を行うことができ、面内膜厚均一性、ステップカバレジ及び膜質の向上を図るこ とができると!、う効果を有する。  The unit layer post-processing catalyst vapor deposition apparatus of the present invention can switch the gas introduction instantaneously, so that film formation can be performed for each unit layer, and surface treatment can be performed for each unit layer formed. It is possible to improve the uniformity of the in-plane film thickness, the step coverage, and the film quality.
また本発明の単位層ポスト処理成膜方法では、単位層ごとに成膜後、表面処理し ているので、膜厚の面内均一性の向上、ステップカバレッジの向上及び膜質特性の 向上した積層薄膜を形成することができるという効果を有する。  Further, in the unit layer post-processing film forming method of the present invention, since the surface treatment is performed after forming the film for each unit layer, a laminated thin film having improved in-plane uniformity of film thickness, improved step coverage, and improved film quality characteristics. Can be formed.
図面の簡単な説明  Brief Description of Drawings
[0012] [図 1]本発明の実施形態に係る単位層ポスト処理触媒化学蒸着装置を示す概略構 成図である。  FIG. 1 is a schematic configuration diagram showing a unit layer post-processing catalytic chemical vapor deposition apparatus according to an embodiment of the present invention.
[図 2]本実施形態に係る単位層ポスト処理成膜方法のガス供給タイミングチャートの 一例を示す図である。  FIG. 2 is a diagram showing an example of a gas supply timing chart of the unit layer post-processing film forming method according to the present embodiment.
[図 3]ガス供給タイミングチャートを示す図。  FIG. 3 is a view showing a gas supply timing chart.
[図 4]ガス供給タイミングチャートを示す図。  FIG. 4 is a view showing a gas supply timing chart.
[図 5]ガス供給タイミングチャートを示す図。  FIG. 5 is a view showing a gas supply timing chart.
[図 6]ガス供給タイミングチャートを示す図。  FIG. 6 is a view showing a gas supply timing chart.
[図 7]ガス供給タイミングチャートを示す図。  FIG. 7 is a view showing a gas supply timing chart.
[図 8]NH供給のみを変化させた時のステップカバレジ変化を示す図である。  FIG. 8 is a view showing a step coverage change when only NH supply is changed.
3  Three
[図 9]NH供給抑制下でのステップカバレジ改善用添加ガスとしての Hと Nの効果 を比較した図である。 [Figure 9] Effect of H and N as additive gases for improving step coverage under suppression of NH supply FIG.
[図 10]in— situポスト処理圧依存性を示す図である。  FIG. 10 is a graph showing pressure dependence of in-situ post treatment.
[図 11]複合ポスト処理時の水素処理効果を示す図である。  FIG. 11 is a view showing a hydrogen treatment effect at the time of composite post treatment.
[図 12]複合ポスト処理時のガス雰囲気依存性を示す図である。  FIG. 12 is a diagram showing gas atmosphere dependency during composite post processing.
[図 13]積層された Cat- SiN膜の単位膜厚依存性を示す図である。  FIG. 13 is a diagram showing the unit film thickness dependence of a stacked Cat-SiN film.
[図 14]アンモニア抑制の SiH ZNH ZH によるシリコン基板上の SiN膜の組成比  [Figure 14] Composition ratio of SiN film on silicon substrate by ammonia-suppressed SiH ZNH ZH
4 3 2  4 3 2
を示す図であり、（a)は水素ガス表面処理を先行させた場合を示し、（b)はアンモ- ァガス表面処理を先行させた場合を示す。 FIGS. 3A and 3B show a case in which a hydrogen gas surface treatment is prioritized, and FIG. 3B shows a case in which an ammonia gas surface treatment is prioritized.
[図 15]シリコン基板上 50Aの SiN膜上に形成された SiNの組成比を示す図であり、 ( a)は水素ガス表面処理を先行させた場合を示し、 (b)はアンモニアガス表面処理を 先行させた場合を示す。  FIG. 15 is a diagram showing the composition ratio of SiN formed on a 50A SiN film on a silicon substrate, where (a) shows a case where hydrogen gas surface treatment was performed first, and (b) shows an ammonia gas surface treatment. Indicates the case in which
[図 16]ポスト処理時のガス導入順番依存性を示す図である。  FIG. 16 is a diagram showing gas introduction order dependence during post processing.
[図 17]標準 Cat-SiNによる単層膜、適合ィ匕 Cat-SiN単位層単位ポスト処理による 積層膜及び PECVD— SiNによる単層膜の水素含有量を示す図である。  FIG. 17 is a diagram showing the hydrogen content of a single-layer film made of standard Cat-SiN, a laminated film formed by post-processing of a unit-formed Cat-SiN unit, and a single-layer film made of PECVD-SiN.
[図 18]各 Cat-SiN膜の水素含有量を比較する図である。 FIG. 18 is a diagram comparing the hydrogen content of each Cat-SiN film.
[図 19]実施例 1に係る成膜方法と従来の成膜方法との成膜条件を示す図である。  FIG. 19 is a view showing film forming conditions of a film forming method according to Example 1 and a conventional film forming method.
[図 20]実施例 2に係る成膜方法と従来の成膜方法との成膜条件を示す図である。 FIG. 20 is a view showing film forming conditions of a film forming method according to Example 2 and a conventional film forming method.
[図 21]実施例 2に係る成膜方法と従来の成膜方法とによって形成された各シリコン窒 化膜に対する、カバレッジと I-V電気耐圧特性の測定結果を示す図である。 FIG. 21 is a view showing the results of measuring coverage and I-V electric breakdown voltage characteristics of each silicon nitride film formed by the film forming method according to Example 2 and the conventional film forming method.
[図 22]実施例 3に係る成膜方法と従来の成膜方法との成膜条件を示す図である。 FIG. 22 is a view showing film forming conditions of a film forming method according to Example 3 and a conventional film forming method.
[図 23]実施例 3に係る成膜方法と従来の成膜方法とによって形成された各シリコン窒 化膜に対する、膜厚の面内均一性とエッチング液に対する耐食性 (エッチング速度） の測定結果を示す図である。 FIG. 23 shows the measurement results of the in-plane uniformity of the film thickness and the corrosion resistance (etching rate) to an etching solution for each silicon nitride film formed by the film forming method according to Example 3 and the conventional film forming method. FIG.
符号の説明 Explanation of symbols
1 単位層ポスト処理触媒化学蒸着装置  1 Unit layer post-processing catalytic chemical vapor deposition equipment
2 反応容器  2 Reaction vessel
3 原料ガス  3 Source gas
4 ガス導入部 5 基板 4 Gas inlet 5 substrate
6 基板ホルダー  6 Board holder
8 触媒体  8 Catalyst
9 ガス供給多岐管  9 Gas supply manifold
10 反応系  10 Reaction system
11 ガス供給系  11 Gas supply system
13 排気系  13 Exhaust system
15 ガス噴出口  15 Gas outlet
21 シランガス導人ライン  21 Silane gas guide line
23 アンモニアガス導人ライン  23 Ammonia gas guide line
25 水素ガス導入ライン  25 Hydrogen gas introduction line
27 窒素ガス導入ライン  27 Nitrogen gas introduction line
31、 53 手動弁  31, 53 Manual valve
33 マスフローコントローラ  33 Mass Flow Controller
34 第 1空圧式操作弁  34 1st pneumatic control valve
35 第 2空圧式操作弁  35 2nd pneumatic control valve
37 逆止弁  37 Check valve
39 ベントライン  39 Vent line
41 補助ポンプ  41 Auxiliary pump
43 ターボ分子ポンプ  43 Turbo molecular pump
45 圧力制御メインバルブ  45 Pressure control main valve
47 サブバルブ  47 Sub valve
49 真空ゲージ  49 vacuum gauge
51 リリーフバルブ  51 Relief valve
55 ゲートパノレブ  55 Gate Pano Lev
57 ロード、口、ソク室 発明を実施するための最良の形態  57 Road, Mouth, Soku Room Best Mode for Carrying Out the Invention
本発明の単位層ポスト処理触媒化学蒸着装置は、真空排気可能な反応容器内で 抵抗加熱した発熱触媒体の触媒作用を利用して基板上に薄膜を形成する触媒化学 蒸着装置であって、薄膜成分含有ガス及び水素ガスの流量をパルス状に反応容器 内に導入可能なガス供給系と、真空排気かつ圧力制御可能な排気系とを備え、パル ス状に導入された薄膜成分含有ガス及び水素ガスが発熱触媒体に接触し分解し、 基板上で単位層ごとの薄膜を形成し、単位層ごとの薄膜を表面処理して積層薄膜を 形成するものである。 The unit layer post-processing catalytic chemical vapor deposition apparatus of the present invention is used in a reaction vessel capable of evacuating. A catalytic chemical vapor deposition system that forms a thin film on a substrate by utilizing the catalytic action of a resistively heated exothermic catalyst. A gas supply that can introduce the thin film component-containing gas and hydrogen gas into the reaction vessel in a pulsed manner. System and an exhaust system capable of vacuum evacuation and pressure control.The thin film component-containing gas and hydrogen gas introduced in pulse form come into contact with the heat generating catalyst and decompose, forming a thin film for each unit layer on the substrate. Then, a thin film is formed by performing a surface treatment on the thin film for each unit layer.
[0015] 以下、図 1一図 18に基づき、実質的に同一又は対応するものには同一符号を用い て、本発明による単位層ポスト処理触媒化学蒸着装置の好適な実施の形態を説明 する。  Hereinafter, preferred embodiments of the unit layer post-processing catalytic chemical vapor deposition apparatus according to the present invention will be described with reference to FIGS.
図 1は、本発明の実施形態に係る単位層ポスト処理触媒化学蒸着装置を示す概略 構成図である。  FIG. 1 is a schematic configuration diagram showing a unit layer post-processing catalytic chemical vapor deposition apparatus according to an embodiment of the present invention.
本実施形態にカゝかる単位層ポスト処理触媒ィ匕学蒸着装置 1は、反応系 10と、ガス 供給系 11と、排気系 13とを備える。  The unit layer post-treatment catalyzing device 1 according to the present embodiment includes a reaction system 10, a gas supply system 11, and an exhaust system 13.
この単位層ポスト処理触媒ィ匕学蒸着装置 1における反応系 10の反応容器 2内の上 部には、反応容器 2内に原料ガス 3を導入するためのガス導入部 4が設けられており 、反応容器 2内の下部には、ガス導入部 4と対向する位置に基板 5を載置する基板ホ ルダー 6が設けられて!/、る。  In the upper part of the reaction vessel 2 of the reaction system 10 in the unit layer post-treatment catalyzer dangling deposition apparatus 1, a gas introduction part 4 for introducing the raw material gas 3 into the reaction vessel 2 is provided. At the lower part in the reaction vessel 2, a substrate holder 6 for mounting a substrate 5 is provided at a position facing the gas introduction part 4.
[0016] 基板ホルダー 6内には、基板ホルダー 6上に載置される基板 5を所定温度に加熱す るためのヒータ 7が設けられて!/、る。 In the substrate holder 6, a heater 7 for heating the substrate 5 mounted on the substrate holder 6 to a predetermined temperature is provided.
また、反応容器 2内のガス導入部 4と基板ホルダー 6との間のガス導入部 4側には、 ガス導入部 4から導入される原料ガスを加熱して分解するための触媒作用を有する 触媒体 8が設けられている。  In addition, the gas introduction section 4 between the gas introduction section 4 and the substrate holder 6 in the reaction vessel 2 has a catalytic action for heating and decomposing the source gas introduced from the gas introduction section 4. A medium 8 is provided.
ガス導入部 4の触媒体 8側にはガス噴出口 15が設けられており、噴出した原料ガス 3が触媒体 8に直ぐに接触するようになって!/、る。  A gas outlet 15 is provided on the catalyst body 8 side of the gas introduction part 4 so that the ejected raw material gas 3 comes into contact with the catalyst body 8 immediately!
触媒体 8として、本実施形態ではコイル状に巻かれたタングステン細線などの高融 点金属細線を用いている力 これに限らず、例えばイリジウム、レニウム、インジウム、 モリブデン、タンタル及びニオブ等が使用可能であり、さらにこれらの合金でもよい。  In the present embodiment, a high melting point metal wire such as a tungsten wire wound in a coil shape is used as the catalyst body 8. The force is not limited to this.For example, iridium, rhenium, indium, molybdenum, tantalum, niobium, etc. can be used. And further, these alloys may be used.
[0017] ガス導入部 4に接続されたガス供給多岐管 9には、原料ガスとしてのシランガス（Si H )、アンモニアガス (NH )及び水素ガス (H )をそれぞれ供給するガス供給系 11[0017] The gas supply manifold 9 connected to the gas introduction unit 4 has a silane gas (Si H), ammonia gas (NH) and hydrogen gas (H), respectively.
4 3 2 4 3 2
が接続されており、シランガスとアンモニアガスは混合されてガス供給多岐管 9を介し てガス導入部 4に供給される。  Is connected, and the silane gas and the ammonia gas are mixed and supplied to the gas introduction unit 4 through the gas supply manifold 9.
薄膜成分としてシリコンを含む薄膜成分含有ガスとしてはシランガスの他に、ジシラ ン（Si H )、トリシラン（Si H ) ,四フッ化シリコン（SiF )、四塩化シリコン（SiCl )及 As a thin film component-containing gas containing silicon as a thin film component, in addition to silane gas, disilane (SiH), trisilane (SiH), silicon tetrafluoride (SiF), silicon tetrachloride (SiCl) and
2 6 3 8 4 4 びジクロロシラン（SiH C1 )等の Siの水素化物やハロゲン元素含有 Si原料ガスが使 2 6 3 8 4 4 and hydride of Si such as dichlorosilane (SiH C1)
2 2  twenty two
用可能である。  Is available.
[0018] また窒素成分を含有するガスとしてはアンモニアの他に、窒素（N )やヒドラジン (N  [0018] As the gas containing a nitrogen component, in addition to ammonia, nitrogen (N) and hydrazine (N
2  2
H )などの窒素を含む化合物の窒素水素化物が使用可能である。  Nitrogen hydrides of compounds containing nitrogen such as H 2) can be used.
2 4  twenty four
水素ガスの他にアルゴンやヘリウムなどの希ガス及び窒素ガスが使用可能である。 ここで、薄膜成分含有ガスは蒸気を含むものであり、例えば室温で液体のものはキ ャリアガスでパブリングにより蒸気圧が調整された薄膜成分含有ガスとして使用される ガス供給系 11は、原料ガス 3を供給するシランガス導入ライン 21、アンモニアガス 導入ライン 23、水素ガス導入ライン 25及び窒素ガス導入ライン 27を有しており、それ ぞれのラインは手動弁 31、マスフローコントローラ 33、第 1空圧式操作弁 34及び第 2 空圧式操作弁 35により原料ガスの質量流量を設定かつ制御して瞬時に切り換え可 能で、ガス供給多岐管 9に供給されるようになって 、る。  In addition to hydrogen gas, rare gases such as argon and helium and nitrogen gas can be used. Here, the thin-film component-containing gas contains steam. For example, a gas that is liquid at room temperature is a carrier gas used as a thin-film component-containing gas whose vapor pressure has been adjusted by publishing. Gas supply line 21, ammonia gas introduction line 23, hydrogen gas introduction line 25, and nitrogen gas introduction line 27, each of which has a manual valve 31, a mass flow controller 33, and a first pneumatic operation. The mass flow rate of the source gas can be set and controlled instantaneously by the valve 34 and the second pneumatic operation valve 35 and supplied to the gas supply manifold 9.
[0019] 第 1空圧式操作弁 34及び第 2空圧式操作弁 35は設定流量の変動を最小限に抑 えて矩形パルス状の質量流量を反応容器側へ切り換えるものである。 [0019] The first pneumatic operation valve 34 and the second pneumatic operation valve 35 switch the rectangular pulse-shaped mass flow rate to the reaction vessel side while minimizing the fluctuation of the set flow rate.
矩形パルス状の質量流量を反応容器 2側へ流すときは、ガス導入前に第 1空圧式 操作弁 34を開、第 2空圧式操作弁 35を閉にして所定設定流量をベント側へ流して 安定的な質量流量にしてから、第 1空圧式操作弁 34と第 2空圧式操作弁 35との開 閉を瞬時に切り換えることにより矩形状のステップパルス状の質量流量を可能にして いる。  When flowing a rectangular pulse-shaped mass flow to the reaction vessel 2 side, open the first pneumatic operation valve 34 and close the second pneumatic operation valve 35 before introducing gas, and flow a predetermined set flow rate to the vent side. After the mass flow rate is stabilized, the opening and closing of the first pneumatic operation valve 34 and the second pneumatic operation valve 35 are instantaneously switched, thereby enabling a rectangular step pulse mass flow rate.
ベント側ラインに原料ガスが流されるとき、これに対応して窒素ガスが流されるように なっている。図 1中、ベントライン 39の 37は逆止弁を示す。  When the raw material gas flows into the vent line, the nitrogen gas is flown accordingly. In FIG. 1, 37 of the vent line 39 indicates a check valve.
なお、この窒素ガス導入ライン 27は、反応系 10のパージ及び成膜終了後の常圧 復帰等で使用される窒素ガスを供給する。 The nitrogen gas introduction line 27 is connected to the purge of the reaction system 10 and the normal pressure after the film formation. Supply nitrogen gas used for recovery and the like.
排気系 13は、補助排気ポンプ 41と、ターボ分子ポンプ 43と、圧力制御メインノ レ ブ 45と、サブバルブ 47と、真空ゲージ 49とを備え、反応容器 2は真空排気可能にな つている。  The exhaust system 13 includes an auxiliary exhaust pump 41, a turbo molecular pump 43, a pressure control main knob 45, a sub-valve 47, and a vacuum gauge 49, and the reaction vessel 2 can be evacuated.
[0020] なお、 51はリリーフバルブ、 53は手動弁を示し、このラインは常圧復帰の際のベン トラインである。  [0020] Note that 51 indicates a relief valve, 53 indicates a manual valve, and this line is a vent line at the time of normal pressure return.
圧力制御メインバルブ 45は真空ゲージ 49の検出信号に基づ 、て設定圧力になる ようにバルブの開度を制御して反応容器 2内の真空度を制御するようになっている。 反応系 10、ガス供給系 11及び排気系 13は、真空排気やガスの導入に伴うバルブ の開閉や質量流量の設定、触媒体への電流供給等のプロセスシーケンスは図示し な 、コンピュータで制御され、例えば操作パネル力 プロセス条件及びシーケンス処 理などのレシピを設定できるようになつている。  Based on the detection signal of the vacuum gauge 49, the pressure control main valve 45 controls the degree of vacuum in the reaction vessel 2 by controlling the opening of the valve so as to reach a set pressure. The reaction system 10, the gas supply system 11, and the exhaust system 13 are controlled by a computer, and the process sequence of opening / closing valves, setting the mass flow rate, supplying current to the catalyst, and the like in accordance with evacuation and gas introduction is not shown. For example, the user can set recipes such as operation panel power, process conditions and sequence processing.
[0021] なお、図 1中、 55はゲートバルブ、 57はロードロック室を示す。 In FIG. 1, 55 indicates a gate valve, and 57 indicates a load lock chamber.
次に単位層ポスト処理触媒ィ匕学蒸着装置 1の使用方法を説明する。  Next, a method of using the unit layer post-processing catalytic dangling vapor deposition apparatus 1 will be described.
先ず、ロードロック室 57に基板を搬送後、ゲートバルブ 55を介して反応容器 2内に 基板 5を搬入して基板ホルダー 6上に載置する。  First, after transporting the substrate to the load lock chamber 57, the substrate 5 is carried into the reaction container 2 via the gate valve 55 and placed on the substrate holder 6.
次に、反応容器 2内を真空排気しつつ、水素ガスや窒素ガスでパージ後、これらの パージガスで所定圧力に制御する。  Next, the inside of the reaction vessel 2 is evacuated and purged with a hydrogen gas or a nitrogen gas, and then the pressure is controlled to a predetermined pressure with these purge gases.
このとき、ヒータ 7に通電して抵抗加熱し、基板ホルダー 6上の基板 5を所定温度（ 例えば 200°C— 600°C程度）に加熱すると共に、触媒体 (タングステン細線など） 8に 通電して抵抗加熱し、触媒体 8を所定温度 (例えば 1600°C— 1800°C程度）に加熱 しておく。  At this time, the heater 7 is energized to perform resistance heating, the substrate 5 on the substrate holder 6 is heated to a predetermined temperature (for example, about 200 ° C. to 600 ° C.), and the catalyst body (such as a thin tungsten wire) 8 is energized. Then, the catalyst body 8 is heated to a predetermined temperature (for example, about 1600 ° C. to about 1800 ° C.).
[0022] さらに、薄膜成分含有ガスを導入前に第 1空圧式操作弁 34を開に、第 2空圧式操 作弁 35閉にして所定設定流量をベント側へ流して安定的な質量流量にしておく。 そして、第 1空圧式操作弁 34と第 2空圧式操作弁 35との開閉を瞬時に切り換えて、 ガス供給管 9を通してガス導入部 4に原料ガス (シランガスとアンモニアガスの混合ガ ス、及び水素ガス）の質量流量を矩形パルス状に導入し、ガス導入部 4の下面に形 成した複数のガス噴出口 15からこの原料ガスが触媒体 8に向けて噴出する。 これにより、原料ガスが加熱されている触媒体 8によって接触熱分解されて、基板 5 上にシリコン窒化膜が例えば単分子層ごとを単位層として成膜される（以下、このェ 程を成膜工程という）。 [0022] Further, before introducing the gas containing the thin film component, the first pneumatic operation valve 34 is opened, and the second pneumatic operation valve 35 is closed to flow a predetermined set flow rate to the vent side to obtain a stable mass flow rate. Keep it. Then, the opening and closing of the first pneumatic operating valve 34 and the second pneumatic operating valve 35 are instantaneously switched, and the raw material gas (mixed gas of silane gas and ammonia gas, The gas (mass) is introduced in a rectangular pulse shape, and the raw material gas is ejected toward the catalyst 8 from a plurality of gas ejection ports 15 formed on the lower surface of the gas introduction unit 4. As a result, the raw material gas is catalytically thermally decomposed by the heated catalyst 8, and a silicon nitride film is formed on the substrate 5, for example, with a monolayer as a unit layer (hereinafter, this film formation is performed). Process).
[0023] このときの成膜条件は、シランガス (SiH )の流量が 7sccm、アンモニアガス（NH )  The film formation conditions at this time are as follows: a flow rate of silane gas (SiH 4) is 7 sccm, and an ammonia gas (NH 3)
4 3 の流量が 10sccm、水素ガス（H )の流量が 10sccm、反応容器 2内の圧力が lOPa  4 The flow rate of 3 is 10 sccm, the flow rate of hydrogen gas (H) is 10 sccm, and the pressure in the reaction vessel 2 is lOPa.
2  2
、触媒体 8の温度が 1700°Cであり、このときの 1回の例えば 10秒間の成膜工程で、 本実施形態では膜厚が lnmの極薄のシリコン窒化膜を得る。  In this embodiment, the temperature of the catalyst body 8 is 1700 ° C., and in this embodiment, an ultra-thin silicon nitride film having a thickness of 1 nm is obtained in a single film-forming step of, for example, 10 seconds.
そして、引き続きこの 1回の単位層の成膜工程後にガス供給多岐管 9を通してガス 導入部 4に水素ガスを例えば 15秒間導入し、ガス噴出口 15から噴出される水素ガス 力 加熱されている触媒体 8を経由することにより活性化されて基板 5上に供給される これにより、基板 5上に形成されているシリコン窒化膜表面が活性化された水素ガス に晒され、シリコン窒化膜表面の組成が改善される（以下、この工程を一の表面処理 工程という）。  Then, after this single unit layer deposition process, hydrogen gas is introduced into the gas introduction unit 4 through the gas supply manifold 9 for, for example, 15 seconds, and the hydrogen gas ejected from the gas ejection port 15 is heated. Activated by passing through the medium 8 and supplied onto the substrate 5, the surface of the silicon nitride film formed on the substrate 5 is exposed to the activated hydrogen gas, and the composition of the surface of the silicon nitride film is increased. Is improved (hereinafter, this step is referred to as one surface treatment step).
[0024] そして、引き続きこの一の表面処理工程後にガス供給多岐管 9を通してガス導入部 4にアンモニアガスを例えば 15秒間導入し、ガス噴出口 15から噴出されるアンモ- ァガスが、加熱されている触媒体 8を経由することにより活性化されて基板 5上に供給 される。  Then, after this one surface treatment step, ammonia gas is introduced into the gas introduction unit 4 through the gas supply manifold 9 for, for example, 15 seconds, and the ammonia gas ejected from the gas ejection port 15 is heated. It is activated and supplied onto the substrate 5 via the catalyst 8.
この一連のサイクルを繰り返すことにより単位層ごとに表面処理された積層薄膜が 堆積する。  By repeating this series of cycles, a laminated thin film surface-treated for each unit layer is deposited.
このように本実施形態では、瞬時のガス導入の切り換え、圧力制御及び高速真空 排気処理が可能なので、矩形パルス状に薄膜成分含有ガス及び水素ガス等を導入 することができ、例えば 1700°Cの発熱触媒体に接触し分解し、基板上で単位層ごと の薄膜を形成し、その単位層ごとの薄膜に表面処理して積層薄膜を形成することが できる。  As described above, in this embodiment, instantaneous switching of gas introduction, pressure control, and high-speed vacuum evacuation can be performed, so that a thin-film component-containing gas and hydrogen gas can be introduced in a rectangular pulse shape. It can be decomposed by contact with the exothermic catalyst to form a thin film for each unit layer on the substrate, and the thin film for each unit layer can be surface-treated to form a laminated thin film.
[0025] 次に、単位層ポスト処理触媒ィ匕学蒸着装置 1を用いた単位層ごとの単位層ポスト処 理成膜方法について説明する。  Next, a unit layer post-processing film-forming method for each unit layer using the unit layer post-processing catalyzer dangling deposition apparatus 1 will be described.
この単位層ポスト処理成膜方法は、真空排気可能な反応容器内で抵抗加熱した発 熱触媒体の触媒作用を利用して基板上に薄膜を形成する触媒化学蒸着法であって 、薄膜成分含有ガス及び水素ガスの流量をパルス状に導入して発熱触媒体に接触 させて活性種を発生させる活性ィ匕過程と、基板上で単位層ごとの薄膜を形成する成 膜過程と、活性種を含む水素ガスで単位層ごとの薄膜の表面処理をする一の表面 処理過程及び活性種を含む薄膜成分含有ガスで単位層ごとの薄膜の表面処理をす る他の表面処理過程の先後を問わず両方の表面処理をする過程とを備え、成膜後 に表面処理した単位層の薄膜を形成する一連の過程を一サイクルとして、複数のサ イタルを繰り返して、積層された薄膜を形成するものである。 This unit layer post-processing film formation method is a method in which resistive heating is performed in a reaction vessel that can be evacuated. This is a catalytic chemical vapor deposition method for forming a thin film on a substrate by utilizing the catalytic action of a thermal catalyst. An active dangling process for generating a thin film, a film forming process for forming a thin film for each unit layer on a substrate, a surface treatment process for performing a surface treatment of the thin film for each unit layer with hydrogen gas containing an active species, and an active species The surface treatment of the thin film of each unit layer with the gas containing the thin film component containing A series of processes for forming a layer is defined as one cycle, and a plurality of cycles are repeated to form a laminated thin film.
[0026] 以下、詳細に説明する。  Hereinafter, a detailed description will be given.
プロセス条件は 触媒 (Cat)線である W (タングステン）の温度を 1700°C、基板カロ 熱ヒータ温度を 100— 300°Cとし、 8インチ Siウェハを基板として用いる。  The process conditions are as follows: the temperature of the catalyst (Cat) wire, W (tungsten), is 1700 ° C, the substrate heater temperature is 100-300 ° C, and an 8-inch Si wafer is used as the substrate.
例としてシリコン窒化膜について説明する。  A silicon nitride film will be described as an example.
図 2は本実施形態に係る単位層ポスト処理成膜方法のガス供給タイミングチャート の一例を示す図である。  FIG. 2 is a diagram showing an example of a gas supply timing chart of the unit layer post-processing film forming method according to the present embodiment.
図 2を参照して、本実施形態にカゝかる単位層ポスト処理成膜方法は、 SiH ZNH  Referring to FIG. 2, the unit layer post-processing film forming method according to the present embodiment is a SiH ZNH
4 3 4 3
ZH = [7/10/10] sccm, lOPaの条件で単位層 SiNを成膜後に 5秒間排気処ZH = [7/10/10] Exhaust for 5 seconds after depositing the unit layer SiN under the conditions of sccm and lOPa.
2 2
理し、 Hでその場 (in— situ)ポスト処理を行う。  And perform an in-situ post-treatment at H.
2  2
その後再び 5秒間排気処理し、さらに NHで in— situポスト処理を行うことを 1サイク  After that, evacuate again for 5 seconds and then perform in-situ post-treatment with NH for one cycle.
3  Three
ノレとして！/、る。  As a note! /
[0027] このタイミングチャートではシリコン窒化膜の成分ガスである NHでのポスト処理に  [0027] In this timing chart, post-processing is performed using NH, which is a component gas of a silicon nitride film.
3  Three
引き続 ヽて連続して成膜処理を行 ヽ、ポスト処理及び成膜処理を一処理で行って ヽ る。  Subsequently, the film forming process is continuously performed, and the post process and the film forming process are performed in one process.
図 3—図 7はガス供給タイミングチャートの他の例を示す。各共通プロセス条件は発 熱触媒体の温度が 1700°C、圧力が lOPaである。  Figures 3 to 7 show other examples of gas supply timing charts. The common process conditions are as follows: the temperature of the heating catalyst is 1700 ° C and the pressure is lOPa.
図 3は、成膜→水素表面処理→アンモニア表面処理→成膜→' · ·を示す図である また図 4は、成膜→アンモニア表面処理→水素表面処理→成膜→' · ·を示し、 図 5は成膜→水素表面処理→アンモニア表面処理→水素表面処理→成膜→' · ·を 示し、図 6は成膜→アンモニア表面処理→水素表面処理→アンモニア表面処理→ 成膜→· · ·を示し、図 7は成膜→真空排気→水素表面処理→アンモニア表面処理→ 真空排気→成膜→' · ·を示す図である。 Fig. 3 is a diagram showing film formation → hydrogen surface treatment → ammonia surface treatment → film formation → '· · Fig. 4 shows film formation → ammonia surface treatment → hydrogen surface treatment → film formation →' Figure 5 shows film formation → hydrogen surface treatment → ammonia surface treatment → hydrogen surface treatment → film formation → ' Fig. 6 shows film formation-> ammonia surface treatment-> hydrogen surface treatment-> ammonia surface treatment-> film formation-> Fig. 7 shows film formation-> vacuum evacuation-> hydrogen surface treatment-> ammonia surface treatment-> vacuum evacuation-> It is a figure which shows a film → '· · ·.
図 3に示す例では、成膜処理における水素ガス導入と、その後の水素表面処理を 連続して処理し、さらにアンモニア表面処理後、成膜処理におけるアンモニアガス導 入とを連続して処理して 、る。  In the example shown in FIG. 3, the introduction of hydrogen gas in the film formation process and the subsequent hydrogen surface treatment are performed continuously, and after the ammonia surface treatment, the introduction of ammonia gas in the film formation process is performed continuously. RU
[0028] このように成膜処理及び表面処理における原料ガスの導入を一処理で行うと流量 及び圧力の変動を小さく抑えることができる。 [0028] As described above, when the introduction of the raw material gas in the film formation process and the surface treatment is performed in one process, fluctuations in the flow rate and the pressure can be suppressed to a small value.
図 7に示す例では、成膜処理の前後に真空排気して雰囲気残留ガスを一掃するこ とにより、ガスメモリ効果を消滅させている。  In the example shown in FIG. 7, the gas memory effect is extinguished by evacuating the atmosphere before and after the film forming process to remove the residual gas in the atmosphere.
このように成膜の前後で真空排気することによりガス供給の有無を確実にでき、例 えば単分子層ごとの成膜が可能になる。  By evacuating before and after the film formation as described above, the presence / absence of gas supply can be ensured. For example, film formation can be performed for each monolayer.
図 8は、プロセス条件が SiH /H供給を一定（[7ZlO] sccm)に保持したまま、 N  Figure 8 shows that the process conditions maintained the SiH / H supply constant ([7ZlO] sccm),
4 2  4 2
H供給のみを変化させた時のステップカバレジ変化を示したものである。  It shows a step coverage change when only the H supply is changed.
3  Three
図 8に示すように、ステップカバレジ改善が NH供給抑制に対して漸進的ではなく  As shown in Figure 8, step coverage improvement is not gradual
3  Three
、ある限界（[SiH /NH ]供給比率 =一 1Z2程度)を超えて極端に抑制されると破  Breaks when it is extremely suppressed beyond a certain limit ([SiH / NH] supply ratio = about 1Z2)
4 3  4 3
滅的に突然もたらされるが、 NH供給を完全に遮断した [SiH /H ]原料だけによる  Despite a sudden catastrophe, only the [SiH / H] raw material that completely shuts off the NH supply
3 4 2  3 4 2
成膜系（すなわち Cat— CVDによる a— Si成膜系）では再びステップカバレジが劣化 する。  In the film forming system (ie, a-Si film forming system by Cat-CVD), the step coverage deteriorates again.
[0029] また、基板温度設定を上昇させるとステップカバレジ改善が消失する傾向にある。  Further, when the substrate temperature setting is increased, the step coverage improvement tends to disappear.
図 9は、 NH供給抑制下でのステップカバレジ改善用添加ガスとしての Hと Nの  Figure 9 shows H and N as additive gases for improving step coverage under NH supply suppression.
3 2 2 効果を比較した図である。  It is the figure which compared 3 2 2 effects.
図 9で明らかなように、ステップカバレジは添加ガスが窒素よりも水素ガスの方が極 めて良好である。  As is evident from Fig. 9, the step coverage is much better when the added gas is hydrogen gas than nitrogen.
したがって、ステップカバレジの改善のためには、添加ガスの種類として Hが好まし  Therefore, H is preferred as a type of additive gas for improving step coverage.
2 い。  2
図 8及び図 9から、 NH由来の Catラジカル（Cat— NH )と H由来の Catラジカル  Figures 8 and 9 show that the NH-derived Cat radical (Cat-NH) and the H-derived Cat radical
3 3 2  3 3 2
又は H原子 (Cat— H )の競争吸着過程中に介在すると推定される堆積中の表面過 程阻害が、顕著に Siリッチな SiN表面にぉ 、てのみ発生することが示されて 、る様に 見える。 Or surface excess during deposition presumed to be present during the competitive adsorption process of H atoms (Cat-H). It is shown that the more the inhibition occurs, only on the surface of the SiN which is remarkably Si-rich.
[0030] SiN膜 Cat— CVD系において添加 Hの果たす役割のひとつは、 Siリッチな SiN  [0030] SiN film Cat— One of the roles played by added H in the CVD system is Si-rich SiN
2  2
が成膜される [SiH ZNH ]供給条件下でのバックエッチ種の可能性を指摘できる。  Can be pointed out under the [SiH ZNH] supply condition.
4 3  4 3
堆積中の Siリッチ SiN膜表面に発生する余剰 Siは、共存する Cat— H〖こ SiHn(n  Excess Si generated on the surface of the Si-rich SiN film during deposition is coexisted with Cat—H 〖ko SiHn (n
2  2
≤ 4)気相シリルラジカルを生成するエッチング反応の攻撃サイトをただちに提供し、 母層である SiNの堆積にこれと競争的なバックエッチ過程が重畳すると考えられる。  ≤ 4) Immediately provides an attack site for the etching reaction that generates gas-phase silyl radicals, and it is thought that a competitive back-etch process overlaps with the deposition of the mother layer SiN.
[0031] このことは一面では堆積中 SiNの表面過程阻害の発生にほかならず、系の表面過 程律速側への移行を通したステップカバレジ改善の一因になっていると推察される。 [0031] On the one hand, this is supposed to be nothing but the inhibition of the surface process of SiN during the deposition, and also contributes to the improvement of the step coverage through the shift of the system to the surface process rate-limiting side.
SiH C1 (ジクロロシラン； DCS)、 Si CI (へキサクロロジシラン； HCD)、 SiCl (四 SiH C1 (dichlorosilane; DCS), Si CI (hexachlorodisilane; HCD), SiCl (four
2 2 2 6 4 塩化シリコン; TCS)、 SiH F (ジフロロシラン； DFS)、 SiF (四フッ化シリコン; TF 2 2 2 6 4 Silicon chloride; TCS), SiH F (difluorosilane; DFS), SiF (silicon tetrafluoride; TF)
2 2 4  2 2 4
S)等のハロゲン元素含有 Si原料ガスの使用によって酸ィ匕性バックエッチ種を堆積中 に関与させ得る熱 CVD系と異なり、 SiH , Si H等の飽和水素化 Siを Si原料ガスと  Unlike the thermal CVD system, in which an oxidizing back-etch species is involved during deposition by using a halogen-containing Si source gas such as S), saturated hydrogenated Si such as SiH and SiH is used as the Si source gas.
4 2 6  4 2 6
して使用する熱 CVD系では HC1, HFガス等のハロゲン元素含有ガスを別途添カロし ない限り一般に良好なカバレジは得にくいと考えられる。  It is generally considered difficult to obtain good coverage in a thermal CVD system used unless a halogen-containing gas such as HC1 or HF gas is added separately.
[0032] NH供給を極端に抑制した [SiH ZNH /H ]原料による Siリッチ SiN膜 Cat— [0032] Si-rich SiN film made of [SiH ZNH / H] raw material with extremely suppressed NH supply Cat—
3 4 3 2  3 4 3 2
CVD系は、 H力 ^還元性バックエッチ種」として機能できる希少かつ貴重な CVD系  Rare and precious CVD system that can function as "H force ^ reducing back etch species"
2  2
と言える。  It can be said.
このことは、堆積にかかわるラジカルの発生場所を基板から遠く離れた触媒体上に 局在させる、 t 、う Cat-CVDの基本原理と密接に結びつ ヽて 、る様にも見える。  This seems to be closely linked to the basic principle of Cat-CVD, where the radicals involved in deposition are localized on the catalyst body far away from the substrate.
Cat— H2ラジカルの発生にとっては理想的な 2000°C近い超高温を利用できるに もかかわらず発生ラジカルの吸着媒である基板の温度は、膜堆積の表面過程制御に 最適なそれに独立に超低温に設定できることと、 Cat— Hラジカルの基板への輸送  Although an ultra-high temperature close to 2000 ° C, which is ideal for the generation of Cat—H2 radicals, can be used, the temperature of the substrate, which is the adsorbent for the generated radicals, is kept at an extremely low temperature, which is optimal for controlling the surface process of film deposition. Configurable and transport of Cat-H radical to substrate
2  2
媒質である [触媒体 基板]間の気相を放電が存在しな!、「静かな (かつ衝突による 輸送中失活機会の少ない超低圧の)気相」にできるということとがあいまって、堆積中 基板表面で高濃度で安定な Hサーファタタントの形成が促進されるのだろうと推定し ている。  There is no discharge in the gas phase between the medium [catalyst substrate] and the "quiet (and ultra-low pressure gas phase with little chance of deactivation during transportation due to collisions)", It is speculated that the formation of high-concentration and stable H-surfatatant on the substrate surface during deposition may be promoted.
図 10は lnm厚の SiN単位層を約 100層積層した lOOnm厚 SiNの屈折率、単位層 当たりの成膜速度、及び 8インチ基板面内膜厚分布の in— situポスト処理圧依存性を 示す図である。 Figure 10 shows the refractive index and unit layer of lOOnm-thick SiN in which about 100 lnm-thick SiN unit layers are stacked. FIG. 6 is a graph showing the in-situ post-processing pressure dependence of a film forming rate per unit thickness and an 8-inch substrate in-plane film thickness distribution.
[0033] 図 10に示すように、屈折率、成膜速度及び面内膜厚均一性は、処理圧にはほとん ど依存しないもののポスト処理雰囲気（ガス種）、即ちアンモニアガスと水素ガスとの 差異には影響されることが示されて 、る。  As shown in FIG. 10, the refractive index, the film formation rate, and the in-plane film thickness uniformity hardly depend on the processing pressure, but the post-processing atmosphere (gas type), that is, the ammonia gas and hydrogen gas Differences have been shown to be affected.
ここで、ポスト処理雰囲気とは、例えば [A(20秒)→排気（5秒)→NH (10秒) ]で  Here, the post-processing atmosphere is, for example, [A (20 seconds) → exhaust (5 seconds) → NH (10 seconds)]
3  Three
表記される連続的なポスト処理手順のうち「雰囲気 A」に相当するものである。つまり「 雰囲気 A」でのガス種選択にかかわらず NH処理は必ず受けて!/、る。  This corresponds to “atmosphere A” in the continuous post-processing procedure described. In other words, regardless of the gas type selection in “Atmosphere A”, be sure to receive NH treatment!
3  Three
「雰囲気 A」を NHとすることで Cat— NH照射のみで構成される in— situポスト処理  In-situ post-processing consisting only of Cat-NH irradiation by setting "atmosphere A" to NH
3 3  3 3
を適用した時よりも、「雰囲気 A」を Hとして Cat— H照射される期間も設定した複合  Composite with the “Atmosphere A” as H and the duration of Cat-H irradiation set compared to when
2 2  twenty two
的内容のポスト処理を適用した時の方が、屈折率、単位層当たりの成膜速度及び 8ィ ンチ基板面内膜厚分布とも有意に低くなつている。  When the post-processing of the target content is applied, the refractive index, the film formation rate per unit layer, and the film thickness distribution in the plane of the 8-inch substrate are significantly lower.
実際、これらの SiN膜を誘電体とする MIS構造キャパシタで測定されたリーク電流 は、図 11に示すように、 Cat— H照射される期間も設定した複合的なポスト処理を施  In fact, the leakage current measured by these MIS capacitors with the SiN film as the dielectric was subjected to a complex post-processing with the Cat-H irradiation period also set, as shown in Fig. 11.
2  2
して積層した Cat— CVDSiNの方が Cat— NH照射のみのポスト処理によるそれより  -Stacked Cat-CVDSiN is better than post-treatment with Cat-NH irradiation only
3  Three
も少ない。  Also less.
[0034] Siリッチな SiNCat— CVD系における表面過程阻害的なサーファタタントとしての C at— Hの可能性に言及した力 この時の堆積中、表面の余剰 Siの気相シリルラジカ [0034] Si-rich SiNCat-Force mentioning the possibility of Cat-H as a surfatatant that inhibits surface processes in the CVD system. During deposition at this time, surplus Si on the surface is vapor-phase silylradica
2 2
ルへの水素化バックエッチングは、 "余剰 Siの引き抜き"という意味でポスト処理期間 中の SiN組成矯正剤としての Cat-Hの可能性を示唆する。  Hydrogenated back-etching of Cu-H in the sense of "extraction of excess Si" suggests the potential of Cat-H as a SiN composition corrector during post-treatment.
2  2
上記の結果は、不足して!/、る Nを補填する「ポスト窒化」だけでなく過剰な Siを除去 する「Si引き抜き」も Siリッチ SiN膜の組成矯正手段として有効であることを示して 、る 様に見える。  The above results show that not only is there a shortage, but also that `` post-nitriding '', which compensates for N, as well as `` Si extraction '', which removes excess Si, is also effective as a means for correcting the composition of Si-rich SiN films. Looks like
図 12は Cat-H照射と Cat— NH照射を併用する"複合ポスト処理"時のガス雰囲  Figure 12 shows the gas atmosphere during "combined post-treatment" using both Cat-H irradiation and Cat-NH irradiation.
2 3  twenty three
気の照射順番カ^ーク電流に与える影響を示す図である。  It is a figure which shows the influence which the irradiation order of a gas gives to a mark current.
図 12に示すように、順番の影響がほとんどないことよりも（Cat— NH照射を関与さ  As shown in Figure 12, the effect of the order (Cat-NH
3  Three
せず) Cat - H照射のみで構成されるポスト処理の場合は、組成矯正効果が不十分  In the case of post treatment consisting only of Cat-H irradiation, the composition correction effect is insufficient
2  2
であることを示している。 したがって、化学量論組成化には「Si引き抜き」と「ポスト窒化」を併用すべきである 図 13は、プロセス条件が最適化された"複合ポスト処理"を施す単位層ごとの Cat— CVDによる積層 SiN膜のリーク電流の単位層膜厚依存を示す図である。 Is shown. Therefore, “Si extraction” and “post-nitridation” should be used together for stoichiometric composition. Fig. 13 shows the results of Cat-CVD by unit layer applying “composite post-processing” with optimized process conditions. FIG. 9 is a diagram showing the dependence of the leakage current of a stacked SiN film on the unit layer thickness.
図 13に示すように、単位層膜厚が薄くなるにつれてリーク電流が低減して！/ヽる。 したがって、一サイクル当たりの堆積膜厚を薄ぐ好ましくは単分子層を単位として 単位層ごとにポスト処理するほどリーク電流が低減され、電気的特性が良好になる。  As shown in FIG. 13, the leak current decreases as the unit layer thickness decreases! / Puru. Therefore, the smaller the deposited film thickness per cycle is, the more preferably the post-processing is performed for each unit layer in a unit of a monomolecular layer, the more the leak current is reduced and the electrical characteristics are improved.
[0035] 次に本実施形態におけるガス導入の順番にっ 、て説明する。 Next, the order of gas introduction in the present embodiment will be described.
CVD開始時の原料ガスの導入順番は、基板表面上の初期核発生プロセスへの影 響を通して [基板 堆積膜]界面の特性に決定的な影響を与えることが広く知られて いる。  It is widely known that the order in which source gases are introduced at the start of CVD has a decisive effect on the characteristics of the [substrate deposited film] interface through the influence on the initial nucleation process on the substrate surface.
図 14はガス種の違いによる表面処理と SiN膜の膜厚方向元素プロファイルを示す 図である。  FIG. 14 is a diagram showing the surface treatment depending on the gas type and the elemental profile in the thickness direction of the SiN film.
図 14に示した例は、 30nm厚の単層 SiN膜を [SiH /NH /H ]原料の Cat— CV  In the example shown in Figure 14, a 30-nm thick single-layer SiN film
4 3 2  4 3 2
Dで成膜する際、成膜開始直前に NH又は Hのみを 30秒間、先行導入させるステ  When forming a film in D, a step in which only NH or H is introduced for 30 seconds immediately before the start of film formation
3 2  3 2
ップを設けたもので、成膜時の各ガス流量は [SiH /NH ZH ] = [7/10/10] SC  The gas flow rate during film formation is [SiH / NH ZH] = [7/10/10] SC
4 3 2  4 3 2
cmであり、顕著に Siリッチではあるが良好なステップカバレジが得られる条件である。 30秒間先行導入時の NH又は H流量も成膜時のそれと同一である。  cm, which is a condition that can obtain excellent step coverage, although notably Si-rich. The NH or H flow rate at the time of 30-second advance introduction is the same as that at the time of film formation.
3 2  3 2
[0036] NH先行導入時には、導入後 30秒が経過した時点で SiHと Hを同時に導入する  [0036] At the time of NH pre-introduction, SiH and H are introduced at the same time 30 seconds after the introduction.
3 4 2  3 4 2
ことで SiN— CVDが開始し、一方、 H先行導入時には 30秒後に SiHと NHを同時  As a result, SiN—CVD starts, while at the time of H advance introduction, SiH and NH
2 4 3 導入することで SiN— CVDが開始する。  2 4 3 Introduction of SiN—CVD starts.
なお、単層 SiN の Cat— CVDでは" 30秒間 NH先行導入"を標準にしている。  In the case of single-layer SiN Cat-CVD, "30 seconds prior NH introduction" is standard.
3  Three
図 14 (a)及び (b)に示すように、成膜時のガス条件が同一であるにもかかわらず、 先行導入するガスの種類によって膜組成が [Si基板 堆積膜]界面付近のみならず 膜厚方向全体にわたって大幅に異なっている。  As shown in Fig. 14 (a) and (b), despite the same gas conditions at the time of film formation, the film composition depends not only on the [Si substrate deposited film] interface but also on the type of gas introduced in advance. It is significantly different over the entire thickness direction.
[0037] さら〖こ、 "H2先行導入"の Cat— CVDでは、成膜時の NH供給を極端に抑制して!/ヽ [0037] Furthermore, in Cat-CVD of "H2 advance introduction", the supply of NH during film formation was extremely suppressed! / ヽ
3  Three
るのにもかかわらず、 NHを十分に供給した Cat— CVD 時と類似したステップカバ  Despite the fact that Cat supplied ample NH—a step cover similar to that during CVD
3  Three
レジの不十分な SiNが堆積し、屈折率の大幅な低下と堆積速度の顕著な (本例では 2倍程度)増大も観測されていて、 NHの分解効率が向上している様に見える。 Insufficient cash register deposits SiN, drastically lowering the refractive index and significantly increasing the deposition rate (in this example, The increase was also observed, and it seems that the decomposition efficiency of NH was improved.
3  Three
図 15 (a)及び (b)は、基板として表面に予め 5nm厚の SiNを成膜した Si基板を使 用した場合を示すが、この下敷き SiNの組成にも依存せず、 Si基板上に直接成膜し た場合と同じ傾向になっている。  Figures 15 (a) and (b) show the case where a Si substrate with a 5-nm-thick SiN film formed on the surface was used as the substrate, but it did not depend on the underlying SiN composition. The tendency is the same as in the case of direct film formation.
[0038] したがって、基板表面の修飾状態や材質には鈍感に堆積膜全体の性質が決定さ れて 、る。 系に関与する「表面」としては生成ラジカルの吸着媒である基板表面の ほかにラジカル生成場所である Cat線表面もある、 t ヽぅ Cat— CVD特有の状況を勘 案するならば、上記現象の起源は基板表面での過程よりも Cat線表面での過程に求 めるべきことが示唆されて 、る。  Accordingly, the properties of the entire deposited film are determined insensitively to the modification state and the material of the substrate surface. The “surface” involved in the system is not only the substrate surface, which is the adsorbent for the generated radicals, but also the surface of the Cat wire, which is where radicals are produced. It has been suggested that the origin of this should be found in the process on the Cat line surface rather than the process on the substrate surface.
[0039] ところで Cat— CVDにお!/、てはこれまで、化学量論組成の SiNを堆積するためには 、例えばプラズマ CVD系に比較して、異常に大きな [NH /SiH ]供給比率 (通常  [0039] By the way, Cat-CVD! / In the past, to deposit SiN of stoichiometric composition, the [NH / SiH] supply ratio was extremely large compared to, for example, the plasma CVD system ( Normal
3 4  3 4
は 20以上程度）にする必要があった力 これは SiHと NHの Cat線上共存時の NH  Is about 20 or more) This is the NH when SiH and NH coexist on the Cat line
4 3  4 3
3分解効率の不可避的低下、ということに帰せられてきた。  3 It has been attributed to the inevitable decrease in decomposition efficiency.
しかし H先行導入時に NHの分解効率が大きく向上するということは、多元ガス系 However, the fact that the decomposition efficiency of NH is greatly improved when H
2 3 twenty three
使用プロセス時の自己被毒によって低下した Cat線の触媒能が、直前の H被曝によ  The catalytic activity of the Cat wire, which was reduced by self-poisoning during the use process, was
2 つて再生できることを示唆して 、る。  It suggests that you can play both.
[0040] この観点からは、循環的な成膜プロセスである単位層ごとの（Layer~by— Layer) C VD系にお 、て、ある単位層成膜直後のポスト処理には次の単位層成膜の前処理の 役割も同時にある、という点に注意が必要である。  [0040] From this viewpoint, in a (Layer-by-Layer) C VD system for each unit layer, which is a cyclic film formation process, the post-processing immediately after the formation of a certain unit layer requires the next unit layer. It should be noted that the pre-treatment of film formation also plays a role.
したがって Cat— H及び Cat— NH導入による連続的なポスト処理は、高ステップ力  Therefore, continuous post-processing with the introduction of Cat-H and Cat-NH requires a high step force.
2 3  twenty three
バレジを得るためには Cat— NH導入処理で終了するのが望ましい。  It is desirable to end with the introduction of Cat-NH in order to obtain the barrage.
3  Three
図 16はポスト処理時のガス導入順番依存性を示す図である。  FIG. 16 is a diagram showing the dependence of the order of gas introduction during post processing.
図 16に示すように、 "in— situポスト処理"中の Cat— Hと Cat— NHの照射順番が  As shown in Fig. 16, the irradiation order of Cat-H and Cat-NH during "in-situ post-processing"
2 3  twenty three
積層 SiNのステップカバレジに与える影響は、屈折率が同一でも順番によりステップ カバレジは一変しており、高ステップカバレジを得るためには単位膜成膜後に後処理 としてアンモニアを導入するのが極めて効果的である。  The effect on the step coverage of the laminated SiN is that the step coverage changes completely depending on the order even if the refractive index is the same.To achieve a high step coverage, it is extremely effective to introduce ammonia as a post-process after forming a unit film. It is.
[0041] 次に本実施形態による膜質について説明する。 Next, the film quality according to the present embodiment will be described.
図 17は標準 Cat-SiNによる単層膜、適合ィ匕 Cat-SiN単位層単位ポスト処理によ る積層膜及び PECVD-SiNによる単層膜の水素含有量を示す図である。 Figure 17 shows a single-layer film made of standard Cat-SiN and a post-process of unit-layer Cat-SiN unit layer. FIG. 4 is a diagram showing the hydrogen content of a laminated film and a single-layer film made of PECVD-SiN.
SiN膜中の水素含有量を FTIR ^ベクトルによって評価した結果、図 17に示すよう に本実施形態の Layer— by— LayerCVDプロセスでは、膜中水素含有量が減少する 十分に NHを供給する従来標準条件の単層 Cat— CVDSiN膜にぉ 、ても含有水  As a result of evaluating the hydrogen content in the SiN film by the FTIR ^ vector, as shown in FIG. 17, in the Layer-by-Layer CVD process of the present embodiment, the hydrogen content in the film is reduced. Conditions for single-layer Cat— CVDSiN films, but also contain water
3  Three
素量が PECVD によるものより少ないことは以前より知られている力 本実施形態の ように各単位層毎に Cat— H照射と Cat— NH照射を併用する" in— situ複合ポスト処  It is a well-known force that the elemental amount is lower than that by PECVD. As in the present embodiment, Cat-H irradiation and Cat-NH irradiation are used in combination for each unit layer.
2 3  twenty three
理" Cat-CVDで成膜すると、さらに減少し、 2. 2 X 1021cm— 3程度にまでなる。 If the film is formed by Cat-CVD, it will further decrease to about 2.2 x 10 21 cm- 3 .
[0042] 図 18は H添加や NH供給抑制及び積層膜構造が含有水素量に与える影響を比 FIG. 18 shows the effect of the addition of H, the suppression of NH supply, and the effect of the laminated film structure on the hydrogen content.
2 3  twenty three
較した図である。  FIG.
図 18から、 Hを添加し、かつ、極端に NH供給を抑制した [SiH /NH /H ]原  From Fig. 18, [SiH / NH / H] source with added H and extremely suppressed NH supply
2 3 4 3 2 料の Cat— CVDでは、 Siリッチ SiN膜を単位層とする積層 SiN膜中の水素含有量は 、 Hを添加せず、かつ、 NHを十分供給した [SiH /NH ]原料を使用する Cat— C In the Cat-CVD method of 2 3 4 3 2, the hydrogen content in the laminated SiN film with the Si-rich SiN film as the unit layer is determined by adding [H] and adding sufficient NH to the [SiH / NH] raw material. Cat— C using
2 3 4 3 2 3 4 3
VDSiN中のそれより、積層膜か単層膜かを問わずむしろ少ない。  Rather less than in VDSiN, regardless of whether it is a laminated or single layer film.
また、原料ガスに H  In addition, H
2添加がない場合、積層膜ィ匕によっても含有水素量低減効果は でない。  2 When there is no addition, the effect of reducing the content of hydrogen is not obtained even by the laminated film.
さらに、 Hを添加し、かつ、極端に NH供給を抑制した [SiH /NH ZH ]原料の  Furthermore, H is added and the supply of NH is extremely suppressed.
2 3 4 3 2 2 3 4 3 2
Cat— CVDでは、 Siリッチ SiN膜であっても単層厚膜では水素含有量が逆に増大し 最も多くなる。 In Cat-CVD, the hydrogen content of single-layer thick films, even for Si-rich SiN films, increases conversely and is highest.
[0043] 以上の説明から明らかなように水素ガスによる表面処理過程が余剰 Siの弓 Iき抜き 処理であり、アンモニアガスによる表面処理力 を補填する添加処理であるといえ、こ のような処理を複合ィ匕したプロセスにより膜厚の均一性及び膜質の向上を図ることが できる。  As is apparent from the above description, the surface treatment process using hydrogen gas is a surplus Si bow I punching process and an addition process for supplementing the surface treatment power with ammonia gas. The uniformity of the film thickness and the film quality can be improved by the process of compounding the above.
また一サイクルの最終過程をアンモニアガスによる表面処理をすることによりステツ プカバレジが格段によくなる。  Also, the final process of one cycle is treated with ammonia gas to make the step coverage much better.
このように本実施形態にカゝかる単位層ポスト処理成膜方法では、面内膜厚均一性、 ステップカバレジ及び膜質の良好な薄膜を形成することができる。  As described above, the unit layer post-process film forming method according to the present embodiment can form a thin film having good in-plane film thickness uniformity, step coverage, and film quality.
実施例 [0044] 次に、実施例について説明する。 Example Next, examples will be described.
(実施例 1)  (Example 1)
実施例 1では、図 1を参照して、 lOPaの減圧下、ヒータ 7に通電して抵抗加熱し、基 板ホルダー 6上の基板 5を例えば 200°Cに加熱すると共に、触媒体 (タングステン細 線など） 8に通電して抵抗加熱し、触媒体 8を 1700°Cに加熱している。  In Example 1, referring to FIG. 1, the heater 7 was energized and heated by resistance under a reduced pressure of lOPa to heat the substrate 5 on the substrate holder 6 to, for example, 200 ° C. (Electrical wire, etc.) 8 is heated by resistance, and the catalyst 8 is heated to 1700 ° C.
成膜条件は、図 19に示すように、シランガス（SiH )の流量が 7sccm、アンモニア  As shown in FIG. 19, the film formation conditions are as follows: a flow rate of silane gas (SiH) is 7 sccm,
4  Four
ガス（NH )の流量が 10sccm、水素ガス（H )の流量が 10sccm、反応容器 2内の圧  The flow rate of gas (NH 2) is 10 sccm, the flow rate of hydrogen gas (H 2) is 10 sccm,
3 2  3 2
力が 10Pa、触媒体 8の温度が 1700°Cであり、このときの 1回の 10秒間の成膜工程 で、本実施例では膜厚が lnmの極薄のシリコン窒化膜を得る。  The force is 10 Pa, the temperature of the catalyst body 8 is 1700 ° C., and in this case, in this embodiment, a thin film of silicon nitride having a thickness of lnm is obtained by one film forming process for 10 seconds.
図 2に示したタイミングチャートで、成膜工程、一及び他の表面処理工程を 1サイク ルとし、この 1サイクルの成膜工程、一及び他の表面処理工程を連続して本実施例で は 50回繰り返して、最終的に総膜厚が 50nmのシリコン窒化膜を形成した。  In the timing chart shown in FIG. 2, the film forming step, one and other surface treatment steps are one cycle, and this one cycle of the film formation step, one and other surface treatment steps are continuously performed in this embodiment. By repeating 50 times, a silicon nitride film having a total thickness of 50 nm was finally formed.
総膜厚が 50nmのシリコン窒化膜に対して、フーリエ変換赤外分光光度計 (FTIR) で測定したシリコン窒化膜中の水素濃度 (水素含有量）は 2 X 1021atomZcm3であ つた o For a silicon nitride film with a total thickness of 50 nm, the hydrogen concentration (hydrogen content) in the silicon nitride film measured by Fourier transform infrared spectrophotometer (FTIR) was 2 × 10 21 atomZcm 3 o
[0045] これに対し、従来の方法のように一度の成膜工程で成膜された膜厚が 50nmのシリ コン窒化膜に対して、フーリエ変換赤外分光光度計 (FTIR)で測定したこのシリコン 窒化膜中の水素濃度は 7 X 1021atomZcm3であった。 On the other hand, a silicon nitride film having a thickness of 50 nm formed in a single film forming step as in the conventional method was measured by a Fourier transform infrared spectrophotometer (FTIR). The hydrogen concentration in the silicon nitride film was 7 × 10 21 atomZcm 3 .
なお、このときの従来の成膜条件は、図 19に示すように、シランガス（SiH )の流量  The conventional film forming conditions at this time are, as shown in FIG. 19, the flow rate of silane gas (SiH).
4 が 7sccm、アンモニアガス（NH )の流量が 10sccm、水素ガス（H )の流量が lOscc  4 is 7sccm, ammonia gas (NH) flow rate is 10sccm, hydrogen gas (H) flow rate is lOscc
3 2  3 2
m、反応容器 2内の圧力が 10Pa、触媒体 8の温度： 1700°Cであり（これらの条件は、 本発明の実施形態における成膜方法の場合と同じ条件）、このときの 1回の成膜工程 で膜厚が 50nmのシリコン窒化膜を得る。  m, the pressure in the reaction vessel 2 is 10 Pa, and the temperature of the catalyst body 8 is 1700 ° C. (these conditions are the same as those of the film forming method in the embodiment of the present invention). A silicon nitride film with a thickness of 50 nm is obtained in the film forming process.
この結果から明らかなように、本発明の成膜工程、一及び他の表面処理工程を 1サ イタルとし、この 1サイクルの成膜工程、一及び他の表面処理工程を連続して複数回 繰り返して、最終的に所望の膜厚のシリコン窒化膜を得る本願発明に係る成膜方法 によれば、従来の成膜方法で得られるシリコン窒化膜の水素濃度水素濃度の値に対 して大幅に低くなる。 したがって、高電界印加時のリーク電流が増加することもなぐ長期にわたって信頼 性の高い高品位なシリコン窒化膜を提供することができる。 As is evident from the results, the film forming step, one and other surface treatment steps of the present invention are defined as one cycle, and this one cycle of the film forming step, one and other surface treatment steps are continuously repeated a plurality of times. Therefore, according to the film forming method of the present invention for finally obtaining a silicon nitride film having a desired film thickness, the hydrogen concentration of the silicon nitride film obtained by the conventional film forming method is greatly reduced. Lower. Therefore, it is possible to provide a high-quality silicon nitride film having high reliability over a long period without increasing the leakage current when a high electric field is applied.
[0046] 〈実施例 2〉  <Example 2>
実施例 1では、 1回の成膜工程で膜厚が lnmのシリコン窒化膜を成膜し、この成膜 工程、一の表面処理工程及び他の表面処理工程の一サイクルの工程を連続して 50 回繰り返して最終的に膜厚が 50nmのシリコン窒化膜を形成したが、実施例 2では、 実施例 1と同様の成膜方法で、一サイクルの工程で膜厚が lnmのシリコン窒化膜を 成膜し、この一サイクルの処理工程を連続して 100回繰り返して最終的に膜厚が 10 Onmのシリコン窒化膜を形成した。  In Example 1, a silicon nitride film having a thickness of lnm was formed in one film forming step, and this film forming step, one surface treatment step, and one cycle of another surface treatment step were continuously performed. A silicon nitride film having a thickness of 50 nm was finally formed by repeating 50 times.In the second embodiment, a silicon nitride film having a thickness of 1 nm was formed in one cycle by the same deposition method as in the first embodiment. The film was formed, and this one cycle processing step was continuously repeated 100 times to finally form a silicon nitride film having a thickness of 10 Onm.
このときのプロセス成膜条件は、図 20に示すように、シランガス（SiH )の流量が 7s  At this time, as shown in FIG. 20, the flow rate of the silane gas (SiH 4) was 7 seconds.
4  Four
ccm、アンモニアガス（NH )の流量が 10sccm、水素ガス（H )の流量が 10sccm、  ccm, ammonia gas (NH) flow rate is 10sccm, hydrogen gas (H) flow rate is 10sccm,
3 2  3 2
反応容器 2内の圧力が 10Pa、触媒体 8の温度が 1700°Cであり（これらの条件は、実 施例 1の場合と同じ条件）、このときの 1回の成膜工程で膜厚が lnmのシリコン窒化 膜を得る。  The pressure in the reaction vessel 2 was 10 Pa, and the temperature of the catalyst body 8 was 1700 ° C (these conditions were the same as those in Example 1). Obtain a lnm silicon nitride film.
[0047] また、実施例 2においても、実施例 1と同様に一の表面処理工程では水素ガスを導 入し、他の表面処理工程ではアンモニアガスを導入した。  [0047] In Example 2, as in Example 1, hydrogen gas was introduced in one surface treatment step, and ammonia gas was introduced in the other surface treatment steps.
実施例 2による成膜方法で得られた総膜厚が lOOnmのシリコン窒化膜の、ステップ カバレッジ（％)と電流 電圧 (I-V)電気耐圧特性 (MV/cm)を測定したところ、図 2 1に示すような測定結果、即ち、シリコン窒化膜のサイドカバレッジが 72%,ボトム力 バレッジが 90%、 I V電気特性耐圧が 4. 8MVZcmと得られた。  The step coverage (%) and the current-voltage (IV) withstand voltage characteristics (MV / cm) of the silicon nitride film having a total film thickness of 100 nm obtained by the film forming method according to Example 2 were measured. As a result of the measurement, the side coverage of the silicon nitride film was 72%, the bottom force coverage was 90%, and the withstand voltage of the IV electric characteristics was 4.8 MVZcm.
また、実施例 2の成膜方法に対する比較のために、従来の方法のように一度の成 膜工程で成膜された膜厚が lOOnmのシリコン窒化膜に対して、カバレッジ（％)と電 流 電圧 (I-V)電気特性耐圧 (MV/cm)を測定したところ、図 21に示すような測定 結果、シリコン窒化膜のサイドカバレッジが 72%,ボトムカバレッジが 90%、 I V電気 特性耐圧が 0. lMVZcm以下と得られた。  For comparison with the film forming method of Example 2, the coverage (%) and the current were compared for a 100 nm thick silicon nitride film formed in a single film forming process as in the conventional method. When the voltage (IV) withstand voltage (MV / cm) was measured, as shown in Fig. 21, the side coverage of the silicon nitride film was 72%, the bottom coverage was 90%, and the IV withstand voltage was 0.1mVZcm. It was obtained as follows.
[0048] なお、このときの成膜条件は、図 20に示すように、シランガス（SiH )の流量が 7scc  As shown in FIG. 20, the flow rate of the silane gas (SiH 4) was 7 sccm.
4  Four
m、アンモニアガス（NH )の流量が 10sccm、水素ガス（H )の流量が 10sccm、反  m, the flow rate of ammonia gas (NH) is 10 sccm, the flow rate of hydrogen gas (H) is 10 sccm,
3 2  3 2
応容器 2内の圧力が 10Pa、触媒体 8の温度が 1700°Cであり（これらの条件は、実施 例 2における成膜方法の場合と同じ条件）、このときの 1回の成膜工程で膜厚が ΙΟΟη mのシリコン窒化膜を得る。 The pressure inside the reaction vessel 2 was 10 Pa and the temperature of the catalyst 8 was 1700 ° C (these conditions Under the same conditions as in the case of the film forming method in Example 2), a silicon nitride film having a thickness of ΙΟΟη m is obtained in one film forming step.
この結果力も明らかなように、上記した成膜工程、一及び他の表面処理工程を 1サ イタルとし、この 1サイクルの成膜工程、一の表面処理工程、他の表面処理工程を連 続して複数回繰り返して、最終的に所望の膜厚のシリコン窒化膜を得る本願発明に 係る成膜方法による方が、従来の成膜方法で得られるシリコン窒化膜に対して、ステ ップカバレッジが向上し、かつ、 I V電気耐圧特性も向上した。  As is clear from the results, the above-mentioned film forming step, one and other surface treatment steps are regarded as one cycle, and this one cycle of the film forming step, one surface treatment step and other surface treatment steps are continuously performed. The film formation method according to the present invention, in which a silicon nitride film having a desired film thickness is finally obtained by repeating a plurality of times, has improved step coverage over the silicon nitride film obtained by the conventional film formation method. In addition, the IV withstand voltage characteristics have also been improved.
[0049] 〈実施例 3〉 <Example 3>
実施例 3では、実施例 2と同様の成膜方法で、 1回の成膜工程で膜厚が lnmのシリ コン窒化膜を成膜し、この成膜工程、一の表面処理工程、他の表面処理工程を連続 して 100回繰り返して最終的に膜厚が lOOnmのシリコン窒化膜を形成した。  In the third embodiment, a silicon nitride film having a thickness of lnm is formed in one film forming step by the same film forming method as the second embodiment, and this film forming step, one surface treatment step, and other The surface treatment process was continuously repeated 100 times to finally form a silicon nitride film having a thickness of 100 nm.
このときの成膜条件は、図 22に示すように、シランガス（SiH )の流量が 7sccm、ァ  At this time, as shown in FIG. 22, the film formation conditions were such that the flow rate of silane gas (SiH) was 7 sccm,
4  Four
ンモユアガス（NH )の流量が 10sccm、水素ガス（H )の流量が 10sccm、反応容器  The flow rate of ammonia gas (NH) is 10sccm, the flow rate of hydrogen gas (H) is 10sccm,
3 2  3 2
2内の圧力が 10Pa、触媒体 8の温度が 1700°Cであり（これらの条件は、実施例 2に おける成膜方法の場合と同じ条件）、このときの 1回の 10秒間の成膜工程で、実施例 3では膜厚が lnmの極薄のシリコン窒化膜を得る。  The pressure in 2 was 10 Pa and the temperature of the catalyst body 8 was 1700 ° C (these conditions were the same as those in the film forming method in Example 2). In the process, in Example 3, an extremely thin silicon nitride film having a thickness of 1 nm is obtained.
そして、成膜されたこの膜厚が lOOnmのシリコン窒化膜の、膜厚の面内均一性とバ ッファード弗酸によるエッチング速度を測定したところ、図 23に示すような測定結果、 即ち、面内均一性が ±4%、エッチング速度が 2nmZminと得られた。  Then, when the in-plane uniformity of the film thickness and the etching rate by buffered hydrofluoric acid of the formed silicon nitride film having a thickness of 100 nm were measured, the measurement results as shown in FIG. The uniformity was ± 4% and the etching rate was 2nmZmin.
[0050] また、実施例 3の成膜方法に対する比較のために、従来の方法のように一度の成 膜工程で成膜された膜厚が lOOnmのシリコン窒化膜に対して、膜厚の面内均一性と ノ ッファード弗酸によるエッチング速度を測定したところ、図 6に示すような測定結果 、即ち、面内均一性が ± 10%、エッチング速度が 6nmZminが得られた。 [0050] For comparison with the film forming method of Example 3, a silicon nitride film having a film thickness of 100 nm in a single film forming process as in the conventional method was compared with a silicon nitride film having a film thickness of 100 nm. When the in-plane uniformity and the etching rate with noffered hydrofluoric acid were measured, the measurement results shown in FIG. 6, that is, ± 10% in-plane uniformity and an etching rate of 6 nm Zmin were obtained.
なお、このときの成膜条件は、図 22に示すように、シランガス（SiH )の流量が 7scc  At this time, as shown in FIG. 22, the film formation conditions were such that the flow rate of silane gas (SiH) was 7 sccc.
4  Four
m、アンモニアガス（NH )の流量が 100sccm、水素ガス（H )の流量が Osccm、反  m, the flow rate of ammonia gas (NH) is 100 sccm, the flow rate of hydrogen gas (H) is Osccm,
3 2  3 2
応容器 2内の圧力が 10Pa、触媒体 8の温度が 1700°Cであり、このときの 1回の成膜 工程で膜厚が lOOnmのシリコン窒化膜を得る。  The pressure in the reaction vessel 2 is 10 Pa, the temperature of the catalyst body 8 is 1700 ° C., and a silicon nitride film having a thickness of 100 nm is obtained in one film forming step.
[0051] この結果から明らかなように、成膜工程、一の表面処理工程、他の表面処理工程を 1サイクルとし、この 1サイクルの工程を連続して複数回繰り返して、最終的に所望の 膜厚のシリコン窒化膜を得る本願発明に係る成膜方法による方が、従来の成膜方法 で得られるシリコン窒化膜に対して、膜厚の面内均一性の向上を図ることができ、ま た、エッチング液に対する耐食性の向上も図ることができた。 As is apparent from the results, the film forming step, one surface treatment step, and another surface treatment step One cycle is performed, and the process of the one cycle is repeated a plurality of times continuously to finally obtain a silicon nitride film having a desired film thickness. The in-plane uniformity of the film thickness of the silicon nitride film can be improved, and the corrosion resistance to the etchant can be improved.
なお、上記した本発明に係るシリコン窒化膜の成膜方法において、 1サイクルの成 膜工程、一の表面処理工程、他の表面処理工程を連続して複数回繰り返して行なう 際に、 1サイクルでの成膜工程、一の表面処理工程、他の表面処理工程の各処理時 間、及びこの 1サイクルの繰り返し回数は任意に設定して行なうことができる。  In the method of forming a silicon nitride film according to the present invention described above, when one cycle of the film forming step, one surface treatment step, and another surface treatment step are continuously and repeatedly performed a plurality of times, The processing times of the film forming step, one surface treatment step, and other surface treatment steps, and the number of repetitions of one cycle can be set arbitrarily.
[0052] また、この 1サイクルでの成膜工程、一の表面処理工程、他の表面処理工程との間 の移行時に反応容器 2内の圧力を任意に調整するようにしてもよい。 [0052] Further, the pressure in the reaction vessel 2 may be arbitrarily adjusted during the transition between the film forming step, one surface treatment step, and another surface treatment step in this one cycle.
さらに、この 1サイクルでの成膜工程後の一の表面処理工程、他の表面処理工程を 交互に複数回繰り返すようにしてもょ 、。  Further, one surface treatment step and another surface treatment step after the film formation step in this one cycle may be alternately repeated a plurality of times.
産業上の利用可能性  Industrial applicability
[0053] 本発明の単位層ポスト処理触媒化学蒸着装置及び単位層ポスト処理成膜方法で は、単分子層を単位とする積層された成膜を形成することができ、膜厚面内均一性、 ステップカバレジ及び膜質の良好な薄膜を形成するのに有用である。 In the unit layer post-processing catalytic chemical vapor deposition apparatus and the unit layer post-processing film forming method of the present invention, a stacked film can be formed in units of monomolecular layers, and the in-plane uniformity of the film thickness can be obtained. It is useful for forming a thin film with good step coverage and film quality.

Claims

請求の範囲 The scope of the claims
[1] 真空排気可能な反応容器内で抵抗加熱した発熱触媒体の触媒作用を利用して基 板上に薄膜を形成する触媒ィ匕学蒸着装置であって、  [1] A catalytic drier vapor deposition apparatus that forms a thin film on a substrate by utilizing the catalytic action of an exothermic catalyst body that is resistance-heated in a reaction vessel that can be evacuated,
薄膜成分含有ガス及び水素ガスの流量をパルス状に上記反応容器内に導入可能 なガス供給系と、真空排気かつ圧力制御可能な排気系とを備え、  A gas supply system capable of introducing the flow rates of the thin film component-containing gas and the hydrogen gas into the reaction vessel in a pulsed manner, and an exhaust system capable of evacuating and controlling the pressure,
上記パルス状に導入された薄膜成分含有ガス及び水素ガスが上記発熱触媒体に 接触し分解し、上記基板上で単位層ごとの薄膜を形成し、その単位層ごとの薄膜に 表面処理して積層薄膜を形成する単位層ポスト処理触媒化学蒸着装置。  The thin film component-containing gas and the hydrogen gas introduced in a pulse form come into contact with the exothermic catalyst to be decomposed, form a thin film for each unit layer on the substrate, and perform surface treatment on the thin film for each unit layer for lamination. Unit layer post-processing catalytic chemical vapor deposition equipment for forming thin films.
[2] 前記表面処理が、活性種を含むシリコンを除く薄膜成分含有ガスによる表面処理 及び活性種を含む水素ガスによる表面処理の 、ずれか、或!、は両方であることを特 徴とする請求項 1記載の単位層ポスト処理触媒ィヒ学蒸着装置。  [2] The surface treatment is characterized in that the surface treatment with a gas containing a thin film component other than silicon containing an active species and the surface treatment with a hydrogen gas containing an active species are both different or both! 2. The unit layer post-processing catalytic vapor deposition apparatus according to claim 1.
[3] 前記発熱触媒体に水素ガスを照射して触媒能を再生させたことを特徴とする請求 項 1記載の単位層ポスト処理触媒ィヒ学蒸着装置。  3. The unit layer post-processing catalytic vapor deposition apparatus according to claim 1, wherein the exothermic catalyst is irradiated with hydrogen gas to regenerate catalytic activity.
[4] 前記表面処理が、余剰薄膜成分の引き抜き処理及び薄膜成分の直接的な添加処 理のいずれか、或いは両方であることを特徴とする請求項 1記載の単位層ポスト処理 触媒化学蒸着装置。  4. The unit layer post-treatment according to claim 1, wherein the surface treatment is either a treatment for extracting an excess thin film component and a treatment for directly adding a thin film component, or both. .
[5] 前記水素ガスに代えて、窒素ガス及び希ガスのいずれかを用いたことを特徴とする 請求項 1に記載の単位層ポスト処理触媒ィ匕学蒸着装置。  [5] The unit layer post-treatment catalyst-based dagger deposition apparatus according to claim 1, wherein one of a nitrogen gas and a rare gas is used instead of the hydrogen gas.
[6] 前記薄膜成分含有ガスが、シリコンの水素化物及びシリコンのハロゲンィ匕物のいず れかと、窒素及び窒素の水素化物のいずれか、或いは両方とであることを特徴とする 請求項 1記載の単位層ポスト処理触媒化学蒸着装置。 6. The gas according to claim 1, wherein the thin-film component-containing gas is one of a silicon hydride and a silicon halide, and / or nitrogen and / or a nitrogen hydride. Unit layer post-processing catalytic chemical vapor deposition equipment.
[7] 前記表面処理における活性種を含む薄膜成分含有ガスが窒素及び窒素の水素化 物のいずれか、或いは両方であることを特徴とする請求項 1記載の単位層ポスト処理 触媒化学蒸着装置。 7. The unit layer post-processing catalytic chemical vapor deposition apparatus according to claim 1, wherein the thin-film component-containing gas containing an active species in the surface treatment is one or both of nitrogen and hydride of nitrogen.
[8] 真空排気可能な反応容器内で抵抗加熱した発熱触媒体の触媒作用を利用して基 板上に薄膜を形成する触媒化学蒸着法であって、  [8] A catalytic chemical vapor deposition method in which a thin film is formed on a substrate by utilizing the catalytic action of an exothermic catalyst that is resistance-heated in a reaction vessel that can be evacuated,
薄膜成分含有ガス及び水素ガスの流量をパルス状に導入して上記発熱触媒体に 接触させて活性種を発生させる活性ィ匕過程と、基板上で単位層ごとの薄膜を形成す る成膜過程と、活性種を含む水素ガスで単位層ごとの薄膜の表面処理をする一の表 面処理過程及び活性種を含む薄膜成分含有ガスで単位層ごとの薄膜の表面処理を する他の表面処理過程の先後を問わず表面処理をする過程とを備え、 An activation process in which the flow rates of the thin film component-containing gas and the hydrogen gas are introduced in a pulsed form and brought into contact with the exothermic catalyst to generate active species, and a thin film for each unit layer is formed on the substrate. One surface treatment process in which a thin film for each unit layer is treated with hydrogen gas containing an active species, and a surface treatment for a thin film in each unit layer with a gas containing a thin film component containing an active species. Surface treatment regardless of before or after the surface treatment step of
成膜後に表面処理をして単位層の薄膜を形成する一連の過程を一サイクルとして 、複数のサイクルを繰り返して積層された薄膜を形成する単位層ポスト処理成膜方法  A series of processes of forming a thin film of a unit layer by performing a surface treatment after film formation is defined as one cycle, and a unit layer post-process film forming method of forming a laminated thin film by repeating a plurality of cycles.
[9] 前記一の表面処理過程及び他の表面処理過程の!/ヽずれかを一サイクル中に複数 回の処理を繰り返すことを特徴とする請求項 8記載の単位層ポスト処理成膜方法。 9. The unit layer post-process film forming method according to claim 8, wherein the process of repeating one or more of the one surface treatment process and the other surface treatment process is repeated a plurality of times during one cycle.
[10] 前記一の表面処理過程及び他の表面処理過程の!/ヽずれか、或いは両方と、基板 上で単位層ごとの薄膜を形成する成膜過程とが連続して処理されることを特徴とする 請求項 8記載の単位層ポスト処理成膜方法。 [10] It is assumed that either or both of the one surface treatment step and the other surface treatment step and the film formation step of forming a thin film for each unit layer on the substrate are continuously performed. 9. The method for forming a unit layer post-processed film according to claim 8, wherein:
[11] 前記成膜過程、前記一の表面処理過程及び他の表面処理過程の！/ヽずれかの後に 残留ガスを真空排気することを特徴とする請求項 8記載の単位層ポスト処理成膜方 法。 [11] In the film forming process, the one surface treatment process and the other surface treatment process! 9. The unit layer post-processing method according to claim 8, wherein the residual gas is evacuated after the deviation.
[12] 前記一の表面処理過程が、余剰薄膜成分の引き抜き処理をする過程であり、前記 他の表面処理過程が薄膜成分の添加処理をする過程であることを特徴とする請求項 12. The method according to claim 1, wherein the one surface treatment step is a step of extracting a surplus thin film component, and the other surface treatment step is a step of adding a thin film component.
8記載の単位層ポスト処理成膜方法。 8. The unit layer post-processing film forming method according to 8.
[13] 前記一サイクルの最終過程が、活性種を含むシリコンを除く薄膜成分含有ガスで表 面処理する過程であることを特徴とする請求項 8記載の単位層ポスト処理成膜方法。 13. The unit layer post-processing film forming method according to claim 8, wherein the final step of the one cycle is a step of performing a surface treatment with a gas containing a thin film component excluding silicon containing active species.
[14] 前記水素ガスに代えて、窒素ガス及び希ガスのいずれかを用いたことを特徴とする 請求項 8に記載の単位層ポスト処理成膜方法。 14. The unit layer post-processing film forming method according to claim 8, wherein one of a nitrogen gas and a rare gas is used instead of the hydrogen gas.
[15] 前記薄膜成分含有ガスが、シリコンの水素化物及びシリコンのハロゲンィ匕物のいず れかと、窒素及び窒素の水素化物のいずれか、或いは両方とであることを特徴とする 請求項 8記載の単位層ポスト処理成膜方法。 15. The thin film component-containing gas according to claim 8, wherein the gas is one of a silicon hydride and a silicon halide, and either or both of nitrogen and nitrogen hydride. Unit layer post-processing film forming method.
[16] 前記表面処理における活性種を含む薄膜成分含有ガスが、窒素及び窒素の水素 化物のいずれか、或いは両方であることを特徴とする請求項 8記載の単位層ポスト処 理成膜方法。 16. The unit layer post-processing film forming method according to claim 8, wherein the thin-film component-containing gas containing an active species in the surface treatment is one or both of nitrogen and hydride of nitrogen.
[17] 前記薄膜成分含有ガスがモノシランガス及びアンモニアガスであり、前記成膜過程 がシリコン窒化膜を基板上で単位層ごとに形成するものであり、前記他の表面処理 過程が活性種を含むアンモニアガスで単位層ごとのシリコン窒化膜の表面処理をす るものであることを特徴とする請求項 8に記載の単位層ポスト処理成膜方法。 [17] The thin film component-containing gas is a monosilane gas and an ammonia gas, Is that a silicon nitride film is formed for each unit layer on a substrate, and the other surface treatment step is to perform a surface treatment of the silicon nitride film for each unit layer with ammonia gas containing active species. 9. The method for forming a unit layer post-processed film according to claim 8, wherein:
前記一サイクルの最終過程が、活性種を含む薄膜成分含有ガスであるアンモニア ガスで表面処理する過程であることを特徴とする請求項 15— 17のいずれかに記載 の単位層ポスト処理成膜方法。  The unit layer post-processing film forming method according to any one of claims 15 to 17, wherein a final process of the one cycle is a process of performing a surface treatment with ammonia gas which is a thin film component-containing gas containing an active species. .
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